CN106133094A - Bonding sheet - Google Patents

Bonding sheet Download PDF

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Publication number
CN106133094A
CN106133094A CN201580016657.XA CN201580016657A CN106133094A CN 106133094 A CN106133094 A CN 106133094A CN 201580016657 A CN201580016657 A CN 201580016657A CN 106133094 A CN106133094 A CN 106133094A
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China
Prior art keywords
film
layer
resin
bonding sheet
recess
Prior art date
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Granted
Application number
CN201580016657.XA
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Chinese (zh)
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CN106133094B (en
Inventor
加藤挥郎
加藤挥一郎
上村和惠
网野由美子
斋藤慈
土渕晃司
小野义友
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Lintec Corp
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Lintec Corp
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Publication of CN106133094A publication Critical patent/CN106133094A/en
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Publication of CN106133094B publication Critical patent/CN106133094B/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/36—Successively applying liquids or other fluent materials, e.g. without intermediate treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/10—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by other chemical means
    • B05D3/107—Post-treatment of applied coatings
    • B05D3/108—Curing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
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    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
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    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/08—Homopolymers or copolymers of acrylic acid esters
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    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
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    • C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
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    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
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    • C09J7/00—Adhesives in the form of films or foils
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    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
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    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
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    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Laminated Bodies (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

The present invention provides a kind of bonding sheet, it has resin bed on base material or release liner, and the surface (α) with the opposition side, side being provided with described base material or release liner of the most described resin bed has cohesive, described resin bed comprises the multilayer structure making of more than 3 layers, the multilayer structure making of described more than 3 layers comprise the microgranule more than containing 15 mass % containing particulate layer, wherein, described it is formed at beyond the outermost layer of described resin bed containing particulate layer, there is recess on surface (α), and described recess be shaped as amorphous.This bonding sheet has an excellent de-gas that can be readily removable the residual of produced air when being pasted on adherend, and resistant blister and adhesion characteristic the best.

Description

Bonding sheet
Technical field
The present invention relates to bonding sheet.
Background technology
Adhesive phase that common bonding sheet by base material, is formed on this base material and being arranged as required in this bonding Release liner in oxidant layer is constituted, and in use, in the case of being provided with release liner, makes bonding after being peeled off by this release liner Oxidant layer contacts with adherend and pastes.
, such as identifying/decoration, application block the surface protection of use, metallic plate etc. with etc. used viscous For veneer amasss big bonding sheet, when being pasted on adherend, between adhesive phase and adherend, it is susceptible to air Residual, this part forms " bubbling ", there is the problem being difficult to bonding sheet is pasted on adherend well.
In order to solve such problem, For example, Patent Document 1 discloses make the release liner with fine embossed pattern Contact with the surface of adhesive phase, formed so that given pattern configures the groove of given shape artificially on the surface of adhesive phase Bonding sheet.
By using such bonding sheet, " the air residual " that produce when pasting with adherend can be via artificial landform The groove becoming adhesive layer surface is discharged in outside.
Prior art literature
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Application Publication 2001-507732 publication
Summary of the invention
The problem that invention is to be solved
But, the adhesive phase with the groove being configured with given shape with given pattern described in patent documentation 1 grade Bonding sheet there is problems with, be difficult to air-out during the narrow width of groove, during the width width of groove, the most not only surface substrate is recessed Falling into and make degraded appearance, bonding force reduces.
It addition, this bonding sheet is configured with groove with given pattern, the bonding force local at the position being therefore configured with groove is deteriorated, When this bonding sheet is pasted on adherend, it is possible to the stripping from this position occurs.
On the other hand, when peeling off again after this bonding sheet is pasted on adherend, owing to the bonding of this bonding sheet is special Property local different, therefore according to the peeling direction of bonding sheet, have the hidden danger producing cull in adherend.Such as, have In the case of the bonding sheet of the adhesive phase being configured to cancellate groove, likely produce residual during oblique stripping in adherend Glue.
Additionally, when this bonding sheet is carried out punch press process, it is possible to make the configuration pattern of groove and the pattern of punch press process Overlapping.In this case, there is penetraction depth uneven, it is impossible on bonding sheet, suitably forming the problems such as otch.
It addition, generally for making the release liner being arranged at bonding sheet be easily peeled off, sometimes carry out only real to release liner Execute otch and the operation (so-called dorsal fissure processing) of stripping starting point is set.When carrying out this operation, generally that release liner is temporary transient Peel off from bonding sheet, release liner is implemented otch, the most again the adhesive phase of release liner and bonding sheet is carried out layer Pressure.
But, for the bonding sheet described in patent documentation 1, use embossed liner as release liner, therefore exist When being again laminated release liner and adhesive phase, release liner is difficult to follow embossed pattern, it is therefore desirable to prepare to be not carried out Other release liner of embossing processing.
Additionally, have employed following method in patent documentation 1: in order to form fine structure at adhesive phase, embossing is served as a contrast Pad is coated with a binding agent and forms adhesive phase, then method (the so-called transfer being laminated this adhesive phase and base material Rubbing method).But, as above-mentioned base material, if using polyolefin-based substrates etc. to have the base material of low polar surfaces, then the method Enough adaptations cannot be obtained with the interface of adhesive phase at base material.
And, different from the release liner formed by paper, resin molding the release liner formed is difficult in adhesive phase shape Become fine embossed pattern.
It addition, the resistant blister of bonding sheet described in patent documentation 1 is poor, therefore exists and easily produce when at high temperature using The problems such as raw foaming.
It is an object of the invention to provide a kind of bonding sheet, it has and can easily remove when being pasted on adherend The excellent de-gas of the residual air generated, and resistant blister and adhesion characteristic are the best.
The method solving problem
The inventors discovered that, the resin layer surface formed by the multilayer structure making comprised containing particulate layer exist recess and Being shaped as unbodied bonding sheet and can solve above-mentioned problem of this recess, thus complete the present invention.
That is, the present invention provides following [1]～[18].
[1] a kind of bonding sheet, it has resin bed on base material or release liner, and the most described resin bed be provided with The surface (α) of the opposition side, side of described base material or release liner has cohesive, and described resin bed comprises the multilamellar of more than 3 layers Structure, the multilayer structure making of described more than 3 layers comprise the microgranule more than containing 15 mass % containing particulate layer, wherein,
Described it is formed at beyond the outermost layer of described resin bed containing particulate layer,
There is recess on surface (α), and described recess be shaped as amorphous.
[2] bonding sheet described in above-mentioned [1], wherein, described recess is the self-forming by described resin bed and is formed.
[3] above-mentioned [1] or [2] described in bonding sheet, wherein, in the cross section of the thickness direction of described resin bed, described Border containing particulate layer and other layer not with described base material or the plane-parallel of release liner.
[4] above-mentioned [1]～[3] according to any one of bonding sheet, wherein, described recess does not have given pattern.
[5] above-mentioned [1]～[4] according to any one of bonding sheet, wherein, surface (α) exists multiple described recess.
[6] bonding sheet described in above-mentioned [5], wherein, the existence position of the plurality of recess does not have periodically.
[7] above-mentioned [1]～[6] according to any one of bonding sheet, wherein, described containing particulate layer in described base material or stripping There is the intensive part of described microgranule on the horizontal plane direction of material intermittently and there is not the part of microgranule.
[8] above-mentioned [1]～[7] according to any one of bonding sheet, wherein, described microgranule be selected from silicon dioxide granule, In metal oxide particle and montmorillonite more than a kind.
[9] above-mentioned [1]～[8] according to any one of bonding sheet, wherein, the average aggregate particle size of volume of described microgranule is Below 50 μm.
[10] above-mentioned [1]～[9] according to any one of bonding sheet, wherein, it is possible to from exposing surface (α) side on surface Observe by the naked eye the amorphous shape confirming to be present in the described recess on surface (α).
[11] above-mentioned [1]～[10] according to any one of bonding sheet, wherein, described containing other layer beyond particulate layer be By comprising the layer that the resin content as main constituent and microgranule is formed less than the compositions of 15 mass %.
[12] above-mentioned [1]～[11] according to any one of bonding sheet, wherein, described resin bed is formed with multiple structure, Described multiple structure is that lamination mainly contains the layer (X of resin portion (X) successively from the side being provided with base material or release liner β), containing particle fraction (Y) more than 15 mass % containing particulate layer (Y1) and the layer (X that mainly contain resin portion (X) α).
[13] bonding sheet described in above-mentioned [12], wherein, described resin portion (X) cross-links containing selected from metal-chelating species In agent, epoxies cross-linking agent and aziridines cross-linking agent more than a kind.
[14] above-mentioned [12] or [13] described in bonding sheet, wherein, layer (X β) be by containing resin as the group of main constituent The layer that compound (x β) is formed, layer (Y1) is the layer formed by the compositions (y) containing microgranules more than 15 mass %, and layer (X α) is By the layer formed as the compositions (x α) of main constituent containing resin.
[15] manufacture method of a kind of bonding sheet, it is to manufacture the bonding sheet according to any one of above-mentioned [1]～[13] Method, the method at least has following operation (1) and (2),
Operation (1): form the operation of film (x ') and film (y '), described film (x ') by containing resin as main constituent Compositions (x) formed, described film (y ') is formed by the compositions (y) containing microgranules more than 15 mass %,
Operation (2): the operation that the film that makes to be formed in operation (1) (x ') and film (y ') are dried simultaneously.
[16] manufacture method of a kind of bonding sheet, it is the method manufacturing the bonding sheet described in above-mentioned [14], and the method is extremely There is following operation (1A) and (2A) less,
Operation (1A): on base material or release liner successively lamination and form film (x β '), film (y ') and film (x α ') operation, described film (x β ') is formed as the compositions (x β) of main constituent by containing resin, and described film (y ') is by institute The compositions (y) stating microgranule more than containing 15 mass % is formed, described film (x α ') by containing resin as the group of main constituent Compound (x α) is formed,
Operation (2A): make the work that the film (x β ') formed in operation (1A), film (y ') and film (x α ') are dried simultaneously Sequence.
[17] manufacture method of a kind of bonding sheet, it is the method manufacturing the bonding sheet described in above-mentioned [14], and the method is extremely There is following operation (1B) and (2B) less,
Operation (1B): on the layer (X β) mainly containing resin portion (X) being arranged on base material or release liner successively Lamination and form film (y ') and the operation of film (x α '), described film (y ') is by the described microgranule containing more than 15 mass % Compositions (y) formed, described film (x α ') is formed as the compositions (x α) of main constituent by containing resin,
Operation (2B): the operation that the film that makes to be formed in operation (1B) (y ') and film (x α ') are dried simultaneously.
[18] a kind of viscoelastic layer, it comprises the multilayer structure making of more than 3 layers, the multilayer structure making bag of described more than 3 layers Contain containing fine-grained containing particulate layer, wherein,
Described it is formed at beyond the outermost layer of described viscoelastic layer containing particulate layer,
There is recess at least one surface of described viscoelastic layer, and this recess be shaped as amorphous.
The effect of invention
The bonding sheet of the present invention has can be readily removable residual air excellent generated when being pasted on adherend Different de-gas, and resistant blister and adhesion characteristic are the best.
Accompanying drawing explanation
Fig. 1 is the generalized section of this bonding sheet of an example of the structure illustrating bonding sheet of the present invention.
Fig. 2 is this resin of an example of resin layer surface (α) the side shape illustrating that the bonding sheet of the present invention had The generalized section of layer.
Fig. 3 is bowing of this surface (α) of an example of the resin layer surface (α) illustrating that the bonding sheet of the present invention had Depending on schematic diagram.
Fig. 4 is the image during bonding sheet with making in sem observation embodiment 1, and (a) is this bonding sheet Cross-sectional image, (b) is resin layer surface (α) side from this bonding sheet stereo-picture when observing.
Fig. 5 is the image during bonding sheet with making in sem observation embodiment 10, and (a) is this bonding sheet Cross-sectional image, (b) is resin layer surface (α) side from this bonding sheet stereo-picture when observing.
Fig. 6 is the image during bonding sheet with making in sem observation comparative example 1, and (a) is this bonding sheet Cross-sectional image, (b) is resin layer surface (α) side from this bonding sheet stereo-picture when observing.
Symbol description
1a, 1b, 2a, 2b bonding sheet
11 base materials
12 resin beds
12a surface (α)
12b surface (β)
(X) resin portion (X)
(Y) particle fraction (Y)
(X β) mainly contains the layer (X β) of resin portion (X)
(X α) mainly contains the layer (X α) of resin portion (X)
(Y1) layer (Y1) of the particle fraction (Y) of 15 mass % is comprised
13,130,131,132 recess
13a crossover sites
14,14a release liner
50, the square of 501,502,503,504 length of sides 1mm
Detailed description of the invention
In the present invention, such as, " containing XX composition as the YY of main constituent ", " YY mainly formed by XX composition " so Record refer to " in the composition contained by YY, the most composition of content is XX composition ".Become as XX concrete in this record The content divided, more than usually 50 mass % of the total amount (100 mass %) relative to YY, preferably 65～100 mass %, more excellent Elect 75～100 mass %, more preferably 85～100 mass % as.
It addition, in the present invention, such as, " (methyl) acrylic acid " refers to both " acrylic acid " and " methacrylic acid ", its It is the most identical that it is similar to term.
Additionally, for preferred numerical range (such as, the scope of content etc.), the lower limit recorded step by step and higher limit Can be combined independently of one another.Such as, according to " preferably 10～90, more preferably 30～60 " such record, it is possible to So that " preferred lower limit (10) " and " preferred higher limit (60) " are combined and obtain " 10～60 ".
(structure of bonding sheet)
First, the structure of the bonding sheet of the present invention is illustrated.
The bonding sheet of the present invention has resin bed on base material or release liner, and this resin bed comprises the multilamellar of more than 3 layers Structure, the multilayer structure making of described more than 3 layers comprises containing fine-grained containing particulate layer.
Fig. 1 is the generalized section of this bonding sheet of an example of the structure illustrating bonding sheet of the present invention, this bonding sheet It it is an example of the structure with the resin bed being made up of the 3-tier architecture body comprised containing particulate layer.
As the concrete structure of the bonding sheet of one mode of the present invention, can enumerate such as: as shown in Fig. 1 (a) Base material 11 has the bonding sheet 1a of resin bed 12, as shown in Fig. 1 (b), there is on release liner 14 resin bed 12 Bonding sheet 1b.
It addition, for the bonding sheet of the present invention, this resin bed 12 be provided with base material 11 or the one of release liner 14 Surface (α) 12a (following, also referred to as " surface (α) ") of opposition side, side has cohesive.
Therefore, from the viewpoint of operability, as the bonding sheet of a mode of the present invention, preferably have in Fig. 1 institute Fig. 1 (c) or (d) of release liner 14a it is provided with further on surface (α) 12a of the resin bed 12 of bonding sheet 1a or 1b shown Structure as shown bonding sheet 2a, 2b.
It should be noted that in the bonding sheet of a mode of the present invention, being provided with base material 11 or peel off of resin bed 12 Surface (β) 12b (following, also referred to as " surface (β) ") of material 14 side can also have cohesive.By making surface (β) Also there is cohesive, in the case of bonding sheet 1a, the 2a shown in Fig. 1 (a) and (c), resin bed 12 and base material 11 can be made Adaptation is good, in the case of bonding sheet 1b, the 2b shown in Fig. 1 (b) and (d), can make double-sided adhesive sheet.
Resin bed 12 is preferably made up of the multilayer structure making of more than 3 layers.Such as, bonding sheet 1a, 1b, 2a, 2b of Fig. 1 has Being formed with the resin bed 12 of multiple structure, this resin bed 12 is that lamination mainly contains resin successively from base material or release liner side Partly (X) layer (X β), containing fine-grained containing particulate layer (Y1) (following, also referred to as " layer (Y1) ") and mainly contain tree The layer (X α) of fat part (X).
It is formed at beyond the outermost layer of this resin bed 12 it should be noted that this contains particulate layer (Y1).That is, surface (α) and Surface (β) is included in the layer beyond containing particulate layer (Y1).When this contains the outermost layer that particulate layer (Y1) is formed at this resin bed 12, Do not simply fail to obtain enough adhesion characteristics, and outward appearance is the poorest.
It should be noted that above-mentioned layer (X α), above-mentioned layer (Y1) and above-mentioned layer (X β) can be by a kind of compositions shape respectively The individual layers become, it is also possible to be the polylayer forest formed by two or more compositions.
The structure of above-mentioned multilayer structure making is as follows: in the cross section of the thickness direction of resin bed, above-mentioned containing particulate layer (Y1) can be as the bonding sheet of Fig. 1 and base material or the level of release liner with the border of other layer (layer (X α) or layer (X β)) Face is parallel, additionally can also be not parallel and be formed as curve or many sidelines, from the viewpoint of being easily formed recess calmly, the most not with Base material or the plane-parallel of release liner.
Additionally, it is preferred that as bonding sheet 1a～2b of Fig. 1, above-mentioned containing particulate layer (Y1) at base material or the water of release liner There is the intensive part of microgranule intermittently and there is not the part of microgranule in in-plane.
Layer (X β) and layer (X α) are the layers mainly containing resin portion (X) but it also may containing particle fraction (Y).Wherein, In layer (X β) and layer (X α), the content of particle fraction (Y) is independently of one another relative to layer (X β) or gross mass (100 matter of layer (X α) Amount %) it is less than 15 mass %, and less than the content of the resin constituting resin portion (X).
It should be noted that for layer (X β) and layer (X α), in addition to resin portion (X) and particle fraction (Y), Can also have gap (Z) described below.
As the resin content in layer (X β) and layer (X α), relative to layer (X β) or gross mass (100 matter of layer (X α) Amount %), the most usually 50～100 mass %, preferably 65～100 mass %, more preferably 75～100 matter Amount %, more preferably 85～100 mass %, the most preferably 90～100 mass %.
It should be noted that in the present invention, " resin content in layer (X β) and layer (X α) " can be considered as this layer Resin in the resin combination total amount (100 mass % (the most not including retarder thinner)) forming material of (X β) or layer (X α) Content.
It addition, as the fraction of particle of constituent particle part (Y) in layer (X β) and layer (X α), relative to layer (X β) or layer (X Gross mass (100 mass %) α), is separately less than 15 mass %, preferably 0～13 mass %, more preferably 0～ 10 mass %, more preferably 0～5 mass %, the most preferably 0 mass %.
It should be noted that in the present invention, " fraction of particle in layer (X β) and layer (X α) " can be considered as this layer Microgranule in the resin combination total amount (100 mass % (the most not including retarder thinner)) forming material of (X β) or layer (X α) Content.
It addition, above-mentioned layer (X β) and layer (X α) be the most respectively by described below containing resin as the combination of main constituent The layer that thing (x β) or (x α) are formed, more preferably by containing resin as the content of main constituent and microgranule less than 15 mass % The layer that compositions (x β) or (x α) are formed.
(Y1) containing particulate layer of the particle fraction (Y) containing 15 mass % can be the layer being only made up of particle fraction (Y), Can also be to comprise particle fraction (Y) and the layer of resin portion (X), it is also possible to there is gap described below further (Z)。
As the fraction of particle of constituent particle part (Y) in layer (Y1), the gross mass (100 mass %) relative to layer (Y1) It is more than 15 mass %, preferably 20～100 mass %, more preferably 25～90 mass %, more preferably 30～85 matter Amount %, the most preferably 35～80 mass %.
It should be noted that in the present invention, " fraction of particle in layer (Y1) " can also be considered as this layer (Y1) Form the fraction of particle in the total composition (100 mass % (the most not including retarder thinner)) of material.
It addition, as the resin content in layer (Y1), the gross mass (100 mass %) relative to layer (Y1) usually 1～ 85 mass %, preferably 5～80 mass %, more preferably 10～75 mass %, more preferably 20～70 mass %, more enters One step is preferably 25～65 mass %.
It should be noted that in the present invention, " resin content in layer (Y1) " can also be considered as this layer (Y1) Form the resin content in the total composition (100 mass % (the most not including retarder thinner)) of material.
It addition, above-mentioned layer (Y1) is preferably the layer formed by the compositions (y) containing microgranule described below, more preferably The layer formed by the compositions (y) containing 15～100 mass % microgranules.
Recess 13 is there is on surface (α) 12a of the resin bed 12 that the bonding sheet of the present invention is had.
As the distributed architecture of the resin portion (X) in resin bed 12 Yu particle fraction (Y), can be resin portion (X) With particle fraction (Y) essentially uniformly distributed structure, it is also possible to be divided into position that local mainly formed by resin portion (X) and The structure at the main position formed by particle fraction (Y).
It addition, as shown in Fig. 1 (a)～(d), in resin bed 12, can be the position that there is recess 13 on surface (α) Ratio shared by middle particle fraction (Y) is less than the such distribution in other position, it is also possible to the most there is not particle fraction (Y).
On surface (α), there is recess in the resin bed that the bonding sheet of the present invention is had, and this recess be shaped as nothing Setting.
It is not particularly limited it addition, overlook the length of this recess 13 when being present in the recess 13 on surface (α).That is, recess 13 include longer flute profile, shorter concave shape.
It should be noted that the recess 13 being present on surface (α) plays the effect as air drain passageway, for " residual air " that produce when the bonding sheet of the present invention is pasted on adherend is discharged to the outside.
Wherein, in the present invention " being shaped as of recess amorphous ' refer to, overlook or do not have during stereovision circle, only by The given shapes such as the shape (triangle, tetragon etc.) that straight line surrounds, shape does not have systematicness, and the shape of each recess does not has Homophylic recess.
It should be noted that whether the shape of the recess judged on surface (α) is that unbodied principle is, with the naked eye or This recess shapes is dimensionally observed and is judged by digit microscope (multiplying power: 30～100 times).If it should be noted that Flat shape when overlooking this recess from surface (α) side is judged as amorphous, then can be considered as " being shaped as without fixed of this recess Shape ".
Wherein, select 10 and gone up the square area defined (R) that optional length of side is 4mm by surface (α), logical Cross naked eyes or digit microscope (multiplying power: 30～100 times) and overlook (carrying out stereovision as required) from surface (α) side to existence Recess shapes in each region (R) is observed, now, if be present in the arbitrary region in 10 regions selected The shape of the recess in each region is judged as amorphous, then can be considered as " recess on the surface (α) of resin bed be shaped as nothing Setting ".
Can be in the case of shooting area more than digit microscope at this region (R), can be by shooting of adjoining each other The image that multiple images that region carries out shooting and obtains carry out being put together is used for as the image in viewing area (R) State judgement.
It should be noted that in the record of this specification, the digital micrograph used during as variously-shaped observation Mirror, can enumerate such as, the ProductName " Digital Microscope VHX-1000 " of KEYENCE company manufacture, " Digital Microscope VHX-5000 " etc..
The shape from the teeth outwards such as the known transfer having as the bonding sheet described in patent documentation 1 grade by embossed pattern Become the bonding sheet of the adhesive phase to the groove of shaped being pre-designed.Being shaped as to setting of the groove of such bonding sheet Shape, even if being designed so that 1 characteristic in de-gas, outward appearance, adhesion characteristic, the punch press process etc. to the shape of groove Being improved, in most cases other characteristic can reduce.
The present inventor etc. are conceived to such as be favorably improved the shape of the groove of de-gas and be favorably improved adhesion characteristic The shape of the groove required to improve each characteristic in the shape of groove this point different, it was found that make amorphous recess be present in and have Technical meaning on the surface (α) of the resin bed of cohesive.
That is, for the bonding sheet of the present invention, the recess owing to being present on resin layer surface (α) is amorphous, and Define and the various characteristics such as de-gas, outward appearance, adhesion characteristic and punch press process are improved the recess that contribution degree is different, therefore The bonding sheet making these balance of properties be improved well can be made.
It addition, from the viewpoint of making the bonding sheet making de-gas be improved, the unbodied shape of this recess is excellent Choosing can observe by the naked eye from resin layer surface (α) side exposed and recognize.It should be noted that for such as Fig. 1 (c) or Be further provided with on the surface at resin bed 12 (α) 12a as shown in (d) release liner 14a bonding sheet 2a, 2b and Speech, preferably peels off this release liner 14a, and can observe by the naked eye from surface (α) side exposed and recognize.
It addition, this recess is preferably formed by the self-forming of above-mentioned resin bed.
In the present invention, " self-forming " refers to, in the autonomous forming process of resin bed, be formed naturally chaotic The phenomenon of shape, more specifically, is dried the film formed by the compositions forming material as resin bed, in tree In the autonomous forming process of lipid layer, it is formed naturally the phenomenon of chaotic shape.
It should be noted that for the recess shapes formed by the self-forming of resin bed in this wise, by right Drying condition, the kind of composition formed as resin bed in the compositions of material, content is adjusted, it is possible to carry out certain journey The adjustment of degree, but from the transfer by embossed pattern and the groove that formed is different, it may be said that " actually cannot reappear identical Shape ".Accordingly, it can be said that the recess formed by the self-forming of resin bed is unbodied.
It is believed that the forming process of the recess formed by the self-forming of resin bed is as described below.
First, when forming the film formed by compositions, randomly there are microgranule in this film, described compositions contains There is the microgranule forming material as particle fraction (Y).
Here, in the operation making dried coating film, film is internal produces shrinkage stress, draws because there is microgranule being considered The part that the resin-bonded power risen weakens, ruptures in film.Then, the resin around this broken portion flows into because rupturing And the space temporarily produced, thus it is believed that form recess on the surface (α) of resin bed.
It should be noted that in the dry run of film, when in film, generation ruptures, the microgranule that initially there are is arranged It is extruded into other parts, it can thus be assumed that, it is formed with the ratio shared by particle fraction (Y) at the position of recess less than other position.
This recess can be readily formed in the following manner, such as, forms containing of, resin many by the content of microgranule respectively Measure the film of few compositions formation and by the film formed containing the compositions that resin is main constituent, and make these 2 kinds of films same Time be dried.
It is believed that by this 2 coating film being dried after 2 coating films different at the content forming resin simultaneously, When dry, inside film, produce shrinkage stress poor, thus be susceptible to rupturing of film.
It should be noted that from the viewpoint of being easily formed recess calmly, preferably on the basis of following item It is adjusted.It is believed that by the comprehensive function of the factor of these items, recess can be readily formed.I.e., it is easy to formed recessed Described in record in the preferred form of each item in portion this project as hereinafter described.
Kind, composition monomer, molecular weight, content as the resin contained in the compositions forming material of film.
As the kind of cross-linking agent contained in the compositions forming material of film, the kind of solvent.
The formation viscosity of compositions of material, solid component concentration as film.
The shape of microgranule, kind, mass concentration.
The dispersity of microgranule formed in the compositions of material and film, the content of microgranule as film.
The thickness of film to be formed.
The baking temperature of the film formed, drying time.
It should be noted that in the formation of the adhesive phase of common bonding sheet, how there is flat surfaces to be formed For the purpose of adhesive phase, above-mentioned item is appropriately configured.
On the other hand, in the present invention, to form the side that can aid in the recess improving bonding sheet de-gas wittingly Above-mentioned item is set by formula, entirely different with the method for designing of the adhesive phase of common bonding sheet.
Above-mentioned item preferably considers in film to be formed that contained microgranule, the mobility of resin suitably set Fixed.
Such as, by the scope to appropriateness will be adjusted by the viscosity of the more film formed containing fine-grained compositions, no Only can keep the given mobility of microgranule in film, and can moderate inhibition (more containing resin with other film Film) mix.By being adjusted in this wise, for the film more containing resin, have and occur in the horizontal direction Rupture and easily form the tendency of recess.
Its result can not only increase the upper ratio shared by recess formed in surface (α), moreover it is possible to increases interconnective recess Ratio, the bonding sheet with more excellent de-gas can be made.
It addition, in above-mentioned item, preferably to the kind of resin, constitute monomer, molecular weight, the content of resin are carried out suitably Adjust so that there is the viscoelasticity of appropriateness containing the resin contained by the film that this resin is more.
That is, by making hardness (hardness determined by the factor such as viscosity of the viscoelasticity of resin, the coating fluid) appropriateness of film Ground is hardening, can strengthen the shrinkage stress of resin portion (X), thus easily form recess.The hardness of this film is the hardest, and shrinking should Power is the strongest, the most easily produces recess, if but really up to the mark, then coating adaptability reduces.During it addition, the elasticity of resin excessively improves, There is the tendency reduced in the bonding force of the resin bed formed by film.In consideration of it, the most moderately adjust the viscous of resin Elastic.
Can be additionally considered to, by properly selecting microgranule, resin etc., and make the dispersity of microgranule become suitable, can Being adjusted with the self-forming power to the degrees of expansion of the resin layer thickness caused by microgranule, recess, result can be adjusted so as to easily In forming recess on surface (α).
And then, it is considered preferred to the crosslinking rate of the film that formed (or as forming compositions of material) and to above-mentioned Item is appropriately configured.
That is, when the crosslinking rate of film is too fast, it is possible to before recess is formed, film just there occurs solidification.It addition, Film is ruptured and has a significant impact.
For the crosslinking rate of film, can be by suitably setting as the cross-linking agent in the compositions forming material Kind and solvent species, the drying time of film and baking temperature are adjusted.
It should be noted that the recess on the resin layer surface that the bonding sheet of the present invention is had (α) the most do not have to Fixed pattern.Here, " given pattern " refers to that, when being conceived to the shape of a recess, becoming that this recess is had is certain The shape of repetitive.
It addition, obtain well from various balance of properties such as making de-gas, outward appearance, adhesion characteristic and punch press process From the viewpoint of the bonding sheet improved, the preferably shape not by the transfer of embossed pattern of the recess on the surface (α) of resin bed Become, surface that the transfer of described embossed pattern includes the release liner implementing embossed pattern such as presses on resin bed and Formed.
The bonding sheet of the present invention preferably as shown in Fig. 1 (a)～(d), resin bed 12 be provided with base material 11 or peel off material On the surface (α) of the opposition side, side of material 14, there is multiple recess 13.
It addition, the recess 13 being had in the bonding sheet preferred surface (α) of the present invention meets in following important document (I)～(IV) Any more than 1 important document, the recess more preferably meeting important document (I) is to meet any more than 1 in important document (II)～(IV) The recess of important document, the recess further preferably meeting important document (I) is to meet whole important document (II), (III) and the recess of (IV).
Important document (I): above-mentioned recess has the difference of height of more than maximum 0.5 μm.
Important document (II): there is multiple recess on the surface (α) of resin bed, and more than the 95% of the plurality of recess has mutually The shape differed.
Important document (III): surface (α) upper optional length of side is the interior existence 1 of square area defined (Q) of 1mm Individual above above-mentioned recess.
Important document (IV): there is multiple recess on the surface (α) of resin bed, and the position that the plurality of recess exists does not has week Phase property.
Hereinafter, above-mentioned important document (I)～(IV) are described in detail.
＜ important document (I) ＞
Fig. 2 is this tree of an example of the shape of resin layer surface (α) side illustrating that the bonding sheet of the present invention had The generalized section of lipid layer.
Recess 13 as shown in Fig. 2 (a), as common recess shapes, there are 2 mountain part (M1)、(M2), with And valley divides (N).In the present invention, " difference of height " of recess refers to the thickness direction along resin bed 12,2 mountain part (M1)、 (M2Position (m) the highest in) (part (M in mountain in Fig. 2 (a)1) maximal point) with minimum position (n) (Fig. 2 (a) two-story valley part (N) minimal point) the length of difference (h).
It addition, if the situation of Fig. 2 (b) is it is believed that have recess 131 and these 2 recesses of recess 132, described recess 131 There are 2 mountain part (M11)、(M12) and valley divide (N1), described recess 132 has 2 mountain part (M12)、(M13) and Valley divides (N2).In this case, mountain part (M11) maximal point and valley divide (N1) the difference (h of minimal point1) lengths table Show the difference of height of recess 131, mountain part (M13) maximal point and valley divide (N2) the difference (h of minimal point2) length represent recessed The difference of height in portion 132.
In above-mentioned important document (I), " recess " of regulation refers to the depression with the difference of height of more than maximum 0.5 μm.Want as this In part (I) " recess " of regulation, the position with the 0.5 above difference of height of μm may reside in the arbitrary portion of recess, it is not necessary to Zone Full at this recess has this difference of height.
Additionally, it is preferred that there is multiple recess meeting this important document (I).
It should be noted that to whether there is the judgement of multiple recess meeting important document (I) by with ultramicroscope pair Carry out observation in the square area defined (P) of upper optional length of side 5mm in the surface (α) of bonding sheet resin bed to sentence Disconnected, more specifically, judged by the method described in embodiment.
As the maximum of the difference of height of this recess, from the viewpoint of the de-gas improving bonding sheet, keep well From the viewpoint of the viewpoint of the outward appearance of bonding sheet and the shape stability of bonding sheet, more than preferably 1.0 μm and resin bed Below thickness, more than more preferably 3.0 μm and below the thickness of resin bed, more preferably more than 5.0 μm and resin bed Below thickness.
It should be noted that as the maximum in the value of the difference of height of the multiple recesses existed in region (P) and resin The ratio (thickness of the maximum/resin bed of difference of height) of the thickness of layer, preferably 1/100～100/100, more preferably 5/100 ～99/100, more preferably 10/100～96/100, the most preferably 15/100～90/100.
It addition, from the viewpoint of improving the viewpoint of de-gas of bonding sheet and making the cohesive of bonding sheet good, as The meansigma methods of the width of this recess, preferably 1～500 μm, more preferably 3～400 μm, more preferably 5～300 μm.
It should be noted that in the present invention, the width of this recess refers to the distance between the maximum point of 2 mountain parts, In the recess 13 shown in Fig. 2 (a), refer to mountain part (M1) and mountain part (M2) distance L.It addition, recessed shown in Fig. 2 (b) In portion 131, refer to mountain part (M11) and mountain part (M12) distance L1, in recess 132, refer to mountain part (M13) and mountain portion Divide (M12) distance L2。
It addition, when overlooking the bonding sheet of the present invention (when observing from surface), there are at recess the feelings of long limit and minor face Under condition, minor face is referred to as width.
From the viewpoint of improving the viewpoint of de-gas of bonding sheet and making the cohesive of bonding sheet good, as this The ratio (meansigma methods of the maximum/width of difference of height) of the maximum of the difference of height of recess and the meansigma methods of width is (at Fig. 2 (a) In shown recess 13, refer to " h/L "), preferably 1/500～100/1, more preferably 3/400～70/3, more preferably 1/ 60～10/1.
＜ important document (II) ＞
Preferably as above-mentioned important document (II), there is multiple recess in the bonding sheet of the present invention on surface (α), and the plurality of More than the 95% of recess has mutually different shape.
By meeting multiple recesses of this important document (II) in the surface of resin bed (α) upper existence, de-gas, outer can be made The bonding sheet that the various balance of properties such as sight, adhesion characteristic and punch press process are improved well.
It should be noted that in the bonding sheet of a mode of the present invention, as on the surface (α) being present in resin bed The ratio of multiple recesses with different shape, relative to the sum (100%) of the recess being present in surface (α), More preferably more than 98%, more preferably 100%.
In the present invention, if the judgement meeting above-mentioned important document (II) is carried out as follows: use ultramicroscope (multiplying power: 30 ～100 times) the optional length of side upper to the resin layer surface (α) of the bonding sheet as object be 5mm square surrounded Region (P) in the shape of multiple recesses that exists observe respectively, if having the number of the recess of different shape Relative to the sum (100%) of the plurality of recess observed in this region (P) be more than 95% (preferably more than 98%, more It is preferably 100%), then it is judged as YES the bonding sheet meeting above-mentioned important document (II).It should be noted that the shape of above-mentioned multiple recess The observation of shape can be the method that direct ultramicroscope carries out observing under above-mentioned multiplying power, it is also possible to be under above-mentioned multiplying power Ultramicroscope is used to obtain image, then the method for the shape of the multiple recesses detected by an unaided eye shown by this image.It addition, more Specifically, judge based on the method described in embodiment.
Here, " number of the recess with different shape is 100% " refers to that " that observes in region (P) is multiple Recess all has mutually different shape ".
In this manual, recess the most continuously coupled in selected region is counted as " 1 recess ". Wherein, such as, though in selected region exist 2 recesses with other region of this area adjacency in combine and formed Being 1 recess, in this selected region, these 2 recesses still count as recess independently.
＜ important document (III) ＞
Fig. 3 (a) and (b) are of the resin layer surface (α) that the bonding sheet of the mode illustrating the present invention is had The schematic top plan view on this surface (α) of example.As shown in Fig. 3 (a), surface (α) 12a of the resin bed 12 of the bonding sheet of the present invention On there is multiple recess 13,130.
Here, for the bonding sheet of the present invention, preferably as described in above-mentioned important document (III), take up an official post at surface (α) 12a 1 is had with upper recess 13,130 in the square that the length of side is 1mm 50 area defined (Q) that meaning selects.In Fig. 3 (a), There are 8 recesses in this region (Q).
So, by having the above-mentioned recess of more than 1 in the region (Q) on surface (α), removing of bonding sheet can be made Gas improves.
It should be noted that in the present invention, the quantity being present in the recess in the region (Q) on surface (α) is preferably 1 More than individual, consider from above-mentioned viewpoint that on the other hand more preferably more than 2, more preferably more than 3, protect from well From the viewpoint of holding outward appearance and adhesion characteristic, preferably less than 1000, more preferably less than 500.
It addition, from the viewpoint of the de-gas improving bonding sheet, as shown in Fig. 3 (a), a preferably mode of the present invention Surface (α) 12a of resin bed 12 that had of bonding sheet on region (Q) in more than one in the recess 13,130 that exists Extend to boundary line as region (Q) the square that the length of side is 1mm 50 any on one side.
It should be noted that on surface (α) 12a of the resin bed 12 of the bonding sheet shown in Fig. 3 (a), recess 13,130 Extension and crossover sites 13a the most on one side with the square that the length of side is 1mm 50 of the boundary line as region (Q) are total up to 9 positions.
Such recess and the cross part as one side any in the square that the length of side is 1mm of the boundary line of region (Q) The quantity of position is preferably more than 1 position, more than more preferably 2 positions, more preferably more than 3 positions.
It addition, from the viewpoint of making the bonding sheet further increasing de-gas, a preferably mode of the present invention The resin layer surface (α) that had of bonding sheet on region (Q) in the recess that exists more than 1 for extend to continuously Shape in more than 1 other region that the square that the length of side adjacent with this region (Q) is 1mm is surrounded (Q '), more preferably For extending to the shape in more than 2 other regions (Q ') continuously, extend to the most continuously more than 3 other Shape in region (Q ').
Such as, in Fig. 3 (b), the upper optional length of side of surface (α) 12a being conceived to resin bed 12 is the pros of 1mm When shape 50 area defined (Q) is interior, " other region that the square that the length of side adjacent with this region (Q) is 1mm is surrounded (Q ') " refer to what the square 502 that square 501 area defined being 1mm by the length of side (Q ' 1), the length of side are 1mm was surrounded Square 503 area defined (Q ' 3) that region (Q ' 2), the length of side are 1mm and the square 504 that the length of side is 1mm are enclosed The region (Q ' 4) become.
And then, when being conceived to " recess 130 " present on surface (α) 12a of the resin bed 12 shown in Fig. 3 (b), " recess 130 " it is by the recess existed in the square 50 area defined (Q) that the length of side is 1mm, but has and extend to and this region (Q) in square 501 area defined (Q ' 1) that the adjacent length of side is 1mm, the square 502 that the length of side is 1mm is surrounded Shape in square 504 area defined (Q ' 4) that region (Q ' 2) is interior and the length of side is 1mm.
" recess 130 " as shown in Fig. 3 (b), by making the upper existence in surface (α) have not only in region (Q) And extend to the recess of the shape in other region adjacent with this region (Q) (Q '), can be made into and further increase de-gas Bonding sheet.
It addition, the interior recess existed in region (Q) on the surface of resin bed (α) is preferably and extends to the most continuously and be somebody's turn to do Adjacent more than 1 other region, region (Q) (Q '), but also extend to adjacent with other region (Q ') the most continuously The shape in region beyond region (Q) (Q ").
Such as, " recess 130 " shown in Fig. 3 (b) have extend to the most continuously with adjacent region, region (Q) (Q ' 4) shape in the region (Q ' 5) adjacent with region (Q ' 4), but also is extended to the most continuously.
＜ important document (IV) ＞
For the bonding sheet of a mode of the present invention, from obtaining de-gas, outward appearance, adhesion characteristic and punch press process From the viewpoint of the bonding sheet that the balance of properties such as property are improved well, the preferably surface (α) of the resin bed of this bonding sheet Present on the existence position of multiple recesses do not have periodically.
In the present invention, " position that multiple recesses exist does not has periodically " refers to that multiple recess does not have identical repetition Pattern, is in the state of random existence.It is to say, it is described such based on certain systematicness with patent documentation 1 The state of the groove " configured " is different, and groove described in this patent documentation 1 is to be pressed on by the release liner with embossed pattern The groove that the surface of resin bed etc. are formed by the transfer of embossed pattern.
It should be noted that judge whether that the principle of " the existence position of multiple recesses does not have periodically " is, use meat Eye is observed or observes the upper existence of resin layer surface (α) of the bonding sheet as object with digit microscope (multiplying power: 30～100 times) The position of multiple recesses.
Wherein it is possible to select 10 by the square area defined that surface (α) upper optional length of side is 4mm (R), detect by an unaided eye or observe with digit microscope (multiplying power: 30～100 times) exist in each region (R) " multiple recesses Position " judge.That is, in the arbitrary region in 10 selected regions, be present in each region " multiple recesses Position " do not have certain periodic situation can be considered as the bonding sheet of object to meet important document (IV).
It addition, above-mentioned observation can be the method that direct digit microscope carries out observing under above-mentioned multiplying power, it is also possible to It is to use digit microscope to obtain image, then the existence of the multiple recesses detected by an unaided eye shown by this image under above-mentioned multiplying power The method of position.
It addition, from making good being improved of balance of properties such as de-gas, outward appearance, adhesion characteristic and punch press process Bonding sheet from the viewpoint of, the shape of the sticking veneer on the resin layer surface (α) of the bonding sheet of a mode of the present invention is excellent Elect as amorphous.
In the present invention, " sticking veneer on surface (α) " refers on the surface (α) of resin bed except shared by multiple recesses Scope beyond surface, when being to paste with adherend and this adherend laminating face.Fig. 3 (a) is to illustrate that this The schematic top plan view on this surface (α) of one example of the resin layer surface (α) that the bonding sheet of a bright mode is had, " pastes Face " refer to the mesh portion in addition to multiple recesses 13 in surface (α) 12a of the resin bed shown in Fig. 3.
It addition, " amorphous " refers to, the shape of the mesh portion of surface (α) 12a of the resin bed as shown in Fig. 3 (a) that Sample, does not have the specific shapes such as round, shape (triangle, tetragon etc.) that is that only surrounded by straight line, does not have systematicness Shape, what the release liner with embossed pattern pressed on the surface etc. of resin bed formed by the transfer of embossed pattern is viscous Except the such shape of veneer.
In other words, for meeting the bonding sheet of important document (II), it is believed that the sticking veneer on surface (α) be shaped as nothing Setting.
It should be noted that judge whether that the principle of " being shaped as of the sticking veneer on surface (α) is amorphous " is, use meat Eye is observed or is observed as on the resin layer surface (α) of the bonding sheet of object with digit microscope (multiplying power: 30～100 times) The shape of sticking veneer judges.
Wherein it is possible to select the square area defined (R) of optional length of side 4mm on surface (α), use meat " shape of sticking veneer " that eye is observed or observed in each region (R) with digit microscope (multiplying power: 30～100 times) is sentenced Disconnected.That is, in the arbitrary region in 10 selected regions, " shape of sticking veneer " in each region is judged as unbodied In the case of, " being shaped as of the sticking veneer on surface (α) is amorphous " can be considered as.
It addition, the observation of the shape of above-mentioned sticking veneer can be that direct digit microscope is observed under above-mentioned multiplying power Method, it is also possible to be to use digit microscope to obtain image under above-mentioned multiplying power, then detect by an unaided eye shown by this image The method of the shape of sticking veneer.
Hereinafter, each composition of the bonding sheet of the present invention is illustrated.
(base material)
As the base material used in a mode of the present invention, it is not particularly limited, can enumerate such as: paper base material, tree Adipose membrane or sheet, the base material etc. obtained with resin layered paper base material, can be according to the use of the bonding sheet of the present invention a mode Suitably select on the way.
As constitute paper base material paper, can enumerate such as: tissue paper, middle rank paper, full slurrying paper, dipping paper, coated paper, Art paper, template, cellophane etc..
As constituting resin molding or the resin of sheet, can enumerate such as: the vistanex such as polyethylene, polypropylene；Polychlorostyrene The vinyl-based trees such as ethylene, Vingon, polyvinyl alcohol, vinyl-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer Fat；The polyesters trees such as polyethylene terephthalate, polybutylene terephthalate (PBT), polyethylene naphthalate Fat；Polystyrene；Acrylonitrile-butadiene-styrene copolymer；Cellulose triacetate；Merlon；Polyurethane, acrylic acid change The polyurethane resins such as property polyurethane；Polymethylpentene；Polysulfones；Polyether-ether-ketone；Polyether sulfone；Polyphenylene sulfide；Polyetherimide, polyamides The polyimide based resins such as imines；Polyamide-based resin；Acrylic resin；Fluororesin etc..
As the base material obtained with resin layered paper base material, can enumerate with laminated thermoplastic resins such as polyethylene above-mentioned Paper base material and the laminated paper etc. that obtains.
Among these base materials, preferred resin film or sheet, the film more preferably formed by polyester resin or sheet, the most excellent Select the film or sheet being made up of polyethylene terephthalate (PET).
It addition, when the bonding sheet of the present invention being used for the purposes of requirement thermostability, preferably by selected from poly terephthalic acid The film of the resin composition of glycol ester and polyimide based resin or sheet；When for requiring the purposes of weatherability, preferably by selecting The film of the resin composition in polrvinyl chloride, Vingon, acrylic resin and fluororesin or sheet.
The thickness of base material suitably can set, from operability and the sight of economy according to the purposes of the bonding sheet of the present invention Point considers, preferably 5～1000 μm, and more preferably 10～500 μm, more preferably 12～250 μm are further preferably 15～150 μm.
It should be noted that base material can also contain UV absorbent, light stabilizer, antioxidant, anti-quiet further The various additives such as electricity agent, slipping agent, antiblocking agent, coloring agent.
It addition, from the viewpoint of the resistant blister improving the bonding sheet obtained, a mode of the present invention uses Base material is preferably non-breathable base material, specifically, is preferably the base on the surface of above-mentioned resin molding or sheet with metal level Material.
As the metal of this metal level of formation, can enumerate such as: aluminum, stannum, chromium, titanium etc. have the metal of metallic luster.
As the forming method of this metal level, can enumerate such as: utilize the PVD method such as vacuum evaporation, sputtering, ion plating to steam Plate and state the method for metal or use common binding agent to paste the method etc. of the metal forming being made up of above-mentioned metal, preferably Utilize the method that PVD method is deposited with above-mentioned metal.
Additionally, in the case of using resin molding or sheet as base material, from improving and being stacked on these resin moldings or sheet Resin bed adaptation from the viewpoint of, preferably implement to utilize oxidizing process, further provided for contouring method etc. to the surface of resin molding or sheet Surface processes or primary coat processes.
As oxidizing process, can enumerate such as: Corona discharge Treatment method, plasma processing, chromic acid process (wet method), heat Wind process, ozone and ultraviolet treatment with irradiation etc., as further provided for contouring method, can enumerate such as: sand-blast, solvent treatment method etc..
(release liner)
As the release liner used in a mode of the present invention, it is possible to use through the stripping of two-sided lift-off processing Sheet, through the stripping film etc. of one side lift-off processing, coating remover can be set forth on release liner base material and the stripping made From sheet etc..It should be noted that preferably this lift-off processing face is not form the smooth release liner of concaveconvex shape (such as, not Implement the release liner of embossed pattern).
As the base material of release liner, can enumerate such as: the bonding sheet as a mode of the present invention is had Base material use above-mentioned paper base material, resin molding or sheet, the base material etc. obtained with resin layered paper base material.
As remover, can enumerate such as: polysiloxanes resinoid, olefine kind resin, isoprene resinoid, fourth two The heat-resistant powder filler such as vinyl resin, chain alkyl resinoid, alkyd based resin, fluorinated resin etc..
The thickness of release liner is not particularly limited, preferably 10～200 μm, and more preferably 25～170 μm are the most excellent Elect 35～80 μm as.
(resin bed)
The resin bed that the bonding sheet of the present invention is had is made up of the multilayer structure making of more than 3 layers, described more than 3 layers many Laminar structure comprises containing fine-grained containing particulate layer.This contains particulate layer and is formed at beyond the outermost layer of this resin bed.
It addition, for the resin bed that the bonding sheet of the present invention is had, at least this resin bed be provided with base material or The surface (α) of the opposition side, side of release liner has a cohesive, but the side being provided with base material or release liner of this resin bed Surface (β) can also have cohesive.
The resin bed that the bonding sheet of one mode of the present invention is had is preferably except resin portion (X) and particle fraction (Y), beyond, also there is gap (Z).By having gap (Z) in resin bed, the resistant blister of bonding sheet can be made Property improve.
This gap (Z) includes being present in above-mentioned microgranule space each other and is secondary grain at above-mentioned microgranule The space etc. existed in this secondary in the case of son.
It addition, in the case of this resin bed has multiple structure, though resin bed forming process, newly formed after deposit At gap (Z), resin portion (X) the most also can flow into gap (Z), make space disappear, and forms tight part (Z) Resin bed.
But, in the case of the gap (Z) making as mentioned above to be temporarily present in resin bed disappears, due to the present invention The resin bed that had of the bonding sheet of a mode on surface (α), there is recess, therefore, it is possible to obtain de-gas and resistance to The bonding sheet that bubble property is excellent.
It addition, from the viewpoint of the de-gas improving bonding sheet and resistant blister, the bonding of a mode of the present invention The resin bed that sheet the is had storage shear modulus when 100 DEG C is preferably 9.0 × 103More than Pa, more preferably 1.0 × 104Pa Above, more preferably 2.0 × 104More than Pa.
It should be noted that in the present invention, the resin bed storage shear modulus when 100 DEG C refers to by using viscoelastic Property determinator (such as, Rheometrics company manufacture, device name " DYNAMIC ANALYZER RDA II ") with frequency 1Hz The value being measured and record.
The thickness of resin bed is preferably 1～300 μm, more preferably 5～150 μm, more preferably 10～75 μm.
As the bonding force of resin layer surface (α) of bonding sheet of a mode of the present invention, preferably 0.5N/25mm with On, more preferably more than 2.0N/25mm, more preferably more than 3.0N/25mm, the most preferably 4.0N/25mm with On, much further preferably from more than 7.0N/25mm.
It addition, in the case of the surface of resin bed (β) also has cohesive, the bonding force of preferred surface (β) is at above-mentioned model Enclose.
It should be noted that the value of this bonding force of bonding sheet refers to the value recorded according to the method described in embodiment.
＜ resin portion (X) ＞
The resin portion (X) constituting resin bed contains resin as main constituent.
It should be noted that in the present invention, resin portion (X) is to comprise the composition beyond microgranule contained in resin bed Part, be distinguished by with particle fraction (Y) in this.
Resin portion (X) is with resin as main constituent, in addition to the resins, it is also possible to containing cross-linking agent, universal additive.
For the resin content in resin portion (X), the total amount (100 mass %) relative to resin portion (X), logical It is often more than 40 mass %, is preferably more than 50 mass %, is more preferably more than 65 mass %, more preferably 75 mass % Above, further it is preferably more than 85 mass %, more than more preferably 90 mass %, and preferably 100 matter Below amount below %, more preferably 99.9 mass %.
It should be noted that in the present invention, it is also possible to will be as the resin combination forming material of resin portion (X) In the value of resin content be considered as above-mentioned " resin content in resin portion (X) ".
As above-mentioned resin contained in resin portion (X), show bonding from the surface (α) making resin bed to be formed From the viewpoint of property, preferably comprise resin of binding property.
Particularly, as bonding sheet 1a～2b of Fig. 1, resin bed has and depends on from being provided with base material or release liner side In the case of the secondary lamination multiple structure of layer (X β), layer (Y1) and layer (X α), consider from above-mentioned viewpoint, preferably at least layer (X α) contains resin of binding property.
As this resin of binding property, can enumerate such as: acrylic resin, polyurethane based resin, rubber resin, poly- Siloxane resin etc..
In these resin of binding property, good from adhesion characteristic and weatherability, easily on the surface of resin bed to be formed (α), from the viewpoint of forming unbodied recess, acrylic resin is preferably comprised.
Relative to the total amount (100 mass %) of the above-mentioned resin contained by resin portion (X), the content of acrylic resin Preferably 25～100 mass %, more preferably 50～100 mass %, more preferably 70～100 mass %, further It is preferably 80～100 mass %, much further preferably from 100 mass %.
It addition, from easy from the viewpoint of the surface (α) of resin bed to be formed forms unbodied recess, resin portion Divide (X) to preferably comprise the resin with functional group, more preferably comprise the acrylic resin with functional group.
Particularly, as bonding sheet 1a～2b of Fig. 1, resin bed has and depends on from being provided with base material or release liner side In the case of the secondary lamination multiple structure of layer (X β), layer (Y1) and layer (X α), consider from above-mentioned viewpoint, preferably at least layer (Y1) comprise there is the resin of functional group.
This functional group is the group becoming the crosslinking starting point with cross-linking agent, can enumerate such as: hydroxyl, carboxyl, epoxy radicals, Amino, cyano group, ketone group, alkoxysilyl etc., preferably carboxyl.
It should be noted that resin portion (X) is preferably further while containing the above-mentioned resin with functional group Containing cross-linking agent.Particularly in the case of resin bed has above-mentioned multiple structure, preferably at least layer (Y1) is containing above-mentioned tool Have while the resin of functional group possibly together with cross-linking agent.
As this cross-linking agent, can enumerate such as: isocyanates cross-linking agent, epoxies cross-linking agent, aziridines cross-link Agent, metal-chelating species cross-linking agent etc..
Isocyanates cross-linking agent can be enumerated such as: toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, benzene two The aromatic polyisocyanates such as methyl diisocyanate；The aliphatic polyisocyantes such as hexamethylene diisocyanate；Different Fo Er The alicyclic polyisocyanates such as ketone diisocyanate, hydrogenated diphenyl methane diisocyanate；And the contracting two of these compounds Urea body, isocyanuric acid ester body and as with containing active hydrogen low molecular compound (ethylene glycol, propylene glycol, neopentyl glycol, three Hydroxymethyl-propane, Oleum Ricini etc.) the adduct of reactant；Etc..
As epoxies cross-linking agent, can enumerate such as: diglycidyl ether of ethylene glycol, 1,3-bis-(N, N-2-glycidyl Base amino methyl) hexamethylene, N, N, N ', N '-four glycidyl group m-xylene diamine, 1,6 hexanediol diglycidylether, three Hydroxymethyl-propane diglycidyl ether, diglycidylaniline, diglycidyl amine etc..
As aziridines cross-linking agent, can enumerate such as: diphenyl methane-4,4 '-two (1-aziridine Methanamides), three Hydroxymethyl-propane three-β-'-aziridino propionic ester, tetramethylol methane three-β-'-aziridino propionic ester, Toluene-2,4-diisocyanate, 4-bis-(1- Aziridine Methanamide), Persistol, two isophthaloyl-1-(2-methylaziridine), three-1-(2-methyl nitrogen third Pyridine) phosphine, trimethylolpropane tris-β-(2-methylaziridine) propionic ester etc..
Metal-chelating species cross-linking agent can be enumerated: metallic atom is the chelate chemical combination of aluminum, zirconium, titanium, zinc, ferrum, stannum etc. Thing, preferably aluminium chelate compound class cross-linking agent.
As aluminium chelate compound class cross-linking agent, can enumerate such as: acetoacetic acid list oleyl aluminum diisopropyl ester, acetoacetic acid Two oleyl aluminum list isopropyl esters, acetoacetic acid aluminium ethide list isopropyl list oleyl ester, acetoacetic acid list lauryl aluminum diisopropyl Ester, acetoacetic acid list stearyl aluminum diisopropyl ester, acetoacetic acid iso stearyl aluminum diisopropyl ester etc..
It should be noted that these cross-linking agent can be used alone, or combine two or more use.
In the middle of these, from easily from the viewpoint of the surface (α) of resin bed to be formed forms unbodied recess, excellent Select that resin portion (X) comprises in metal-chelating species cross-linking agent, epoxies cross-linking agent and aziridines cross-linking agent a kind with On, more preferably comprise metal-chelating species cross-linking agent, further preferably comprise aluminium chelate compound class cross-linking agent.
Relative to having resin 100 mass parts of functional group, the content of cross-linking agent is preferably 0.01～15 mass parts, more excellent Elect 0.1～10 mass parts, more preferably 0.3～7.0 mass parts as.
It addition, from the viewpoint of the shape retention of multiple recess from the surface (α) making resin bed is good, preferably Resin portion (X) contains metal-chelating species cross-linking agent and epoxies cross-linking agent simultaneously.
In the case of resin portion (X) contains metal-chelating species cross-linking agent and epoxies cross-linking agent, from above-mentioned simultaneously Viewpoint considers, as content ratio [the metal-chelating species cross-linking agent/epoxy of metal-chelating species cross-linking agent with epoxies cross-linking agent Class cross-linking agent], the most preferably 10/90～99.5/0.5, more preferably 50/50～99.0/1.0, further preferably It is 65/35～98.5/1.5, the most preferably 75/25～98.0/2.0.
It addition, resin portion (X) can also contain universal additive.
As universal additive, can enumerate such as: viscosifier, antioxidant, softening agent (plasticizer), antirust agent, pigment, Dyestuff, blocker, reaction promoter, UV absorbent etc..
It should be noted that these universal additives can individually use, or combine two or more use.
In the case of containing these universal additives, relative to resin 100 mass parts, the content of each universal additive is excellent Elect 0.0001～60 mass parts, more preferably 0.001～50 mass parts as.
The above-mentioned resin contained in resin portion (X) can simply be a kind, it is also possible to combines two or more and uses.
The formation material of the resin portion (X) of the resin bed being had as the bonding sheet of the present invention, preferably comprises and has The binding agent of the resin of binding property of functional group, more preferably comprise have functional group acrylic resin (A) (following, be also called for short For " acrylic resin (A) ") acrylic adhesives, further preferably comprise the acrylic resin with functional group And the acrylic adhesives of cross-linking agent (B) (A).
This acrylic adhesives can be any form in solvent-borne type, emulsion-type.
Hereinafter, illustrate as the material institute preferably aforesaid propylene acrylic binder forming resin portion (X).
As the acrylic resin (A) contained in this acrylic adhesives, can enumerate such as: have to be derived from and have The polymer of the construction unit of (methyl) alkyl acrylate of straight or branched alkyl, have to be derived from there is circulus The polymer etc. of the construction unit of (methyl) acrylate.
As the weight average molecular weight (Mw) of acrylic resin (A), preferably 50,000～1,500,000, more preferably 150,000～ 1300000, more preferably 250,000～1,100,000, the most preferably 350,000～900,000.
As acrylic resin (A), preferably comprise and there is construction unit (a1) and the acrylic compounds of construction unit (a2) Copolymer (A1), described construction unit (a1) is derived from (methyl) alkyl acrylate of the alkyl with carbon number 1～18 (a1 ') (following, also referred to as " monomer (a1 ') "), described construction unit (a2) be derived from monomer containing functional group (a2 ') (following, Also referred to as " monomer (a2 ') "), more preferably acrylic copolymer (A1).
Total amount (100 mass %) relative to acrylic resin in acrylic adhesives (A), acrylic copolymer (A1) content is preferably 50～100 mass %, more preferably 70～100 mass %, more preferably 80～100 matter Amount %, the most preferably 90～100 mass %.
It should be noted that the copolymerization mode of acrylic copolymer (A1) is not particularly limited, it can be block copolymerization Any one in thing, random copolymer, graft copolymer.
From improving from the viewpoint of adhesion characteristic, as the carbon number of the alkyl that monomer (a1 ') is had, more preferably 4～12, more preferably 4～8, the most preferably 4～6.
As monomer (a1 '), can enumerate such as: (methyl) acrylic acid methyl ester., (methyl) ethyl acrylate, (methyl) third Olefin(e) acid propyl ester, (methyl) butyl acrylate, (methyl) 2-EHA, (methyl) lauryl acrylate, (methyl) third Olefin(e) acid Arrcostab, (methyl) stearyl acrylate ester etc..
Wherein, preferably (methyl) butyl acrylate, (methyl) 2-EHA, more preferably (methyl) acrylic acid fourth Ester.
Relative to the entire infrastructure unit (100 mass %) of acrylic copolymer (A1), the content of construction unit (a1) Being preferably 50～99.5 mass %, more preferably 60～99 mass %, more preferably 70～95 mass %, the most excellent Elect 80～93 mass % as.
As monomer (a2 '), can enumerate such as: hydroxyl monomer, carboxyl group-containing monomer, containing epoxy based monomers, containing amino Monomer, cyano-containing monomer, ketone group containing monomer, containing alkoxysilyl monomer etc..
Wherein, more preferably carboxyl group-containing monomer.
As carboxyl group-containing monomer, can enumerate: (methyl) acrylic acid, maleic acid, fumaric acid, itaconic acid etc., preferably (first Base) acrylic acid.
Relative to the entire infrastructure unit (100 mass %) of acrylic copolymer (A1), the content of construction unit (a2) Preferably 0.5～50 mass %, more preferably 1～40 mass %, more preferably 5～30 mass %, the most preferably It is 7～20 mass %.
It is derived from beyond above-mentioned monomer (a1 ') and (a2 ') it should be noted that acrylic copolymer (A1) can also have The construction unit (a3) of other monomer (a3 ').
As other monomer (a3 '), can enumerate such as: (methyl) cyclohexyl acrylate, (methyl) benzyl acrylate, (methyl) isobornyl acrylate, (methyl) acrylic acid bicyclopentyl ester, (methyl) acrylic acid dicyclopentenyl ester, (methyl) propylene Acid dicyclopentenyl epoxide ethyl ester, imino group (methyl) acrylate etc. have (methyl) acrylate of circulus, acetic acid Vinyl acetate, acrylonitrile, styrene etc..
Relative to the entire infrastructure unit (100 mass %) of acrylic copolymer (A1), the content of construction unit (a3) Preferably 0～30 mass %, more preferably 0～20 mass %, more preferably 0～10 mass %, the most preferably 0 ～5 mass %.
It should be noted that above-mentioned monomer (a1 ')～(a3 ') can be used alone, or combine two or more use.
For the synthetic method of acrylic copolymer (A1) composition, it is not particularly limited, for example, it is possible to by by raw material Monomer be dissolved in solvent and carry out in the presence of polymerization initiator, chain-transferring agent etc. the method for polymerisation in solution, emulsifying agent, The method that starting monomer carries out emulsion polymerization in aqueous systems is used in the presence of polymerization initiator, chain-transferring agent, dispersant etc. Manufacture.
As the cross-linking agent (B) contained in aforesaid propylene acrylic binder, above-mentioned substance can be enumerated, from making adhesion characteristic From the viewpoint of good viewpoint and the easy resin layer surface (α) in the formation unbodied recess of upper formation, preferably comprise In metal-chelating species cross-linking agent and epoxies cross-linking agent more than a kind, more preferably contains metal-chelating species cross-linking agent, Further preferably containing aluminium chelate compound class cross-linking agent.
It addition, from the viewpoint of the shape retention of the multiple recesses made resin layer surface (α) is good, as crosslinking Agent (B), contains metal-chelating species cross-linking agent and epoxies cross-linking agent the most simultaneously.
Relative to acrylic resin (A) 100 mass parts in aforesaid propylene acrylic binder, the content of cross-linking agent (B) It is preferably 0.01～15 mass parts, more preferably 0.1～10 mass parts, more preferably 0.3～7.0 mass parts.
In the case of being applied in combination metal-chelating species cross-linking agent and epoxies cross-linking agent, hand over as metal-chelating species Connection agent and the content ratio [metal-chelating species cross-linking agent/epoxies cross-linking agent] of epoxies cross-linking agent, be preferably by quality ratio 10/90～99.5/0.5, more preferably 50/50～99.0/1.0, more preferably 65/35～98.5/1.5, further It is preferably 75/25～98.0/2.0.
Do not damaging in the range of effect of the present invention, in the acrylic adhesives used in a mode of the present invention also Universal additive can be contained.As universal additive, above-mentioned additive can be enumerated, and the content of this universal additive is also As mentioned above.
Do not damaging in the range of effect of the present invention, in the acrylic adhesives used in a mode of the present invention also Resin of binding property (such as, polyurethane based resin, rubber resin, the polysiloxanes beyond acrylic resin (A) can be contained Resinoid etc.).
Relative to the total amount (100 mass %) of the resin of binding property contained in acrylic adhesives, acrylic adhesive The content of the acrylic resin (A) in agent is preferably 50～100 mass %, and more preferably 70～100 mass % are the most excellent Elect 80～100 mass %, the most preferably 100 mass % as.
＜ particle fraction (Y) ＞
The particle fraction (Y) constituting resin bed is made up of microgranule.
From improving the de-gas of bonding sheet and the viewpoint of resistant blister and easily on the resin layer surface (α) formed From the viewpoint of forming unbodied recess, as the mean diameter of microgranule, preferably 0.01～100 μm, more preferably 0.05 ～25 μm, more preferably 0.1～10 μm.
As the microgranule used in a mode of the present invention, it is not particularly limited, can enumerate: silicon dioxide granule, Inorganic particulate, the acrylic acid such as metal oxide particle, barium sulfate, calcium carbonate, magnesium carbonate, bead, smectite (smectite) The organic fillers etc. such as Bio-Glas.
In the middle of these microgranules, more than a kind be preferably selected from silicon dioxide granule, metal oxide particle and smectite, More preferably silicon dioxide granule.
The silicon dioxide granule used in one mode of the present invention can be dry silica and wet silica In any one.
It addition, the silicon dioxide granule used in the present invention mode can be having of apparatus responding property functional group Machine compound etc. carried out surface modify and obtain organic decoration silicon dioxide, with the inorganic chemical such as sodium aluminate, sodium hydroxide Thing has carried out surface and has processed and the inorganic modification silicon dioxide that obtains and carrying out with these organic compound and inorganic compound The organic-inorganic that surface processes and obtains is modified silicon dioxide, has been carried out table with organic-inorganic mixing materials such as silane couplers The organic-inorganic that face processes and obtains modifies silicon dioxide etc..
It should be noted that these silicon dioxide granules can be the mixture formed by two or more.
Relative to the total amount (100 mass %) of silicon dioxide granule, the quality of the silicon dioxide in silicon dioxide granule is dense Degree is preferably 70～100 mass %, more preferably 85～100 mass %, more preferably 90～100 mass %.
It addition, from improving the de-gas of bonding sheet and the viewpoint of resistant blister and easily at the resin layer surface formed (α), from the viewpoint of the unbodied recess of upper formation, the volume of the silicon dioxide granule used in a mode of the present invention is put down All secondary particle size are preferably 0.5～50 μm, more preferably 0.5～30 μm, more preferably 0.5～～10 μm, further It is preferably 1～8 μm, in more preferably 1.5～5 μm.
It should be noted that in the present invention, the value of the volume average secondary particle diameter of silicon dioxide granule is to use Multisizer 3 grade the value obtained by utilizing the particle size distribution of coulter counter method.
As oxidized metal particle, can enumerate such as by selected from titanium oxide, aluminium oxide, boehmite, chromium oxide, oxidation Oxidized metal in nickel, copper oxide, titanium oxide, zirconium oxide, Indium sesquioxide., zinc oxide and their composite oxides is formed Particles etc., also include the sol particles formed by these oxidized metals.
As smectite, can enumerate such as: montmorillonite (montmorillonite), beidellite, hectorite, saponite (saponite), humite (Stevensite), nontronite, sauconite etc..
Quality after the resin bed being had by the bonding sheet of the present invention mode heats 30 minutes at 800 DEG C is protected Holdup is preferably 3～90 mass %, and more preferably 5～80 mass %, more preferably 7～70 mass %, the most excellent Elect 9～60 mass % as.
This quality retention can be considered as representing the value of the content (quality %) of the microgranule contained in resin bed.
When this quality retention is more than 3 mass %, de-gas and the bonding sheet of resistant blister excellence can be made.And And, when manufacturing the bonding sheet of the present invention, easily the upper formation in the surface (α) of the resin bed formed meet above-mentioned important document (I)～ (III) multiple recesses.On the other hand, when this quality retention is below 90 mass %, the film-strength of resin bed is high, it is possible to Make resistance to water, the bonding sheet of resistance to chemical reagents excellence.
(manufacture method of bonding sheet)
It follows that the manufacture method of the bonding sheet of the present invention is illustrated.
As the manufacture method of the bonding sheet of the present invention, it is not particularly limited, from productive viewpoint and is easily treating The surface (α) of the resin bed formed is upper form unbodied recess from the viewpoint of, preferably at least have following operation (1) and (2) method, described unbodied recess is to be formed by the self-forming of resin bed.
Operation (1): form the operation of film (x ') and film (y '), described film (x ') by containing resin as main constituent Compositions (x) formed, described film (y ') is formed by the compositions (y) containing above-mentioned microgranule
Operation (2): the operation that the film that makes to be formed in operation (1) (x ') and film (y ') are dried simultaneously
＜ operation (1) ＞
Operation (1) is the operation forming film (x ') and film (y '), described film (x ') by containing resin as main one-tenth The compositions (x) divided is formed, and described film (y ') formed by the compositions (y) containing above-mentioned microgranule.
Compositions (x) is the formation material of resin portion (X), contains above-mentioned resin and cross-linking agent the most simultaneously, it is also possible to Contain above-mentioned universal additive further.
It addition, compositions (y) is the formation material of particle fraction (Y), resin, cross-linking agent, above-mentioned can be contained further Universal additive.These compositionss (y) containing the compositions such as resin also become the formation material of resin portion (X).
(compositions (x))
As the resin contained in compositions (x), the resin constituting above-mentioned resin portion (X) can be enumerated, be preferably tool There are the resin of binding property of functional group, the most above-mentioned acrylic resin (A) with functional group, preferably aforesaid propylene acid Analog copolymer (A1).
Relative to the total amount (100 mass % (the most not including retarder thinner)) of compositions (x), resin in compositions (x) Content be usually more than 40 mass %, be preferably more than 50 mass %, more than more preferably 65 mass %, more preferably More than more than 75 mass %, more than further preferably 85 mass %, much further preferably from 90 mass %, also, it is preferred that It is below below 100 mass %, more preferably 95 mass %.
It addition, as the cross-linking agent contained in compositions (x), the crosslinking contained in above-mentioned resin portion (X) can be enumerated Agent, preferably comprises more than a kind in metal-chelating species cross-linking agent and epoxies cross-linking agent, more preferably contains metal-chelating Species cross-linking agent.
It addition, from the viewpoint of the shape retention of multiple recesses from the surface (α) of the resin bed making formation is good, Preferred resin part (X) contains metal-chelating species cross-linking agent and epoxies cross-linking agent simultaneously.
In the case of compositions (x) contains metal-chelating species cross-linking agent and epoxies cross-linking agent, as combination simultaneously The content ratio of the metal-chelating species cross-linking agent in thing (x) and epoxies cross-linking agent [hand over by metal-chelating species cross-linking agent/epoxies Connection agent], by quality ratio, preferably 10/90～99.5/0.5, more preferably 50/50～99.0/1.0, more preferably 65/35～98.5/1.5, the most preferably 75/25～98.0/2.0.
Relative to resin 100 mass parts contained in compositions (x), the content of cross-linking agent is preferably 0.01～15 mass Part, more preferably 0.1～10 mass parts, more preferably 0.3～7.0 mass parts.
As compositions (x), the most above-mentioned comprising has the acrylic resin (A) of functional group and cross-linking agent (B) Acrylic adhesives, the most above-mentioned acrylic adhesives comprising acrylic copolymer (A1) and cross-linking agent (B).
It should be noted that the details of aforesaid propylene acrylic binder is described above.
Compositions (x) can contain above-mentioned microgranule, but the content of this microgranule is less than 15 mass %, and less than compositions The content of the resin contained in (x).
Relative to the total amount (100 mass % (the most not including retarder thinner)) of compositions (x), concrete fraction of particle is little In 15 mass %, preferably 0～13 mass %, more preferably 0～10 mass %, more preferably 0～5 mass %, more enters One step is preferably 0 mass %.
(compositions (y))
Compositions (y) is the formation material of particle fraction (Y), at least contains the above-mentioned microgranule of more than 15 mass %, but from From the viewpoint of the dispersibility of microgranule, contain microgranule and resin, more preferably while containing this resin further the most simultaneously Containing cross-linking agent.It addition, compositions (y) can also contain universal additive.
It should be noted that these resins, cross-linking agent and universal additive become the formation material of resin portion (X).
As microgranule contained in compositions (y), above-mentioned microgranule can be enumerated, from forming gap resin bed (Z), from the viewpoint of making the bonding sheet that resistant blister is improved, it is preferably selected from silicon dioxide granule, metal-oxide grain In son and smectite more than a kind.
From the sight being prone on the surface (α) of resin bed to be formed the amorphous recess utilizing the self-forming of resin bed and formed Point considers, relative to the total amount (100 mass % (the most not including retarder thinner)) of compositions (y), the microgranule in compositions (y) Content be more than 15 mass %, preferably 20～100 mass %, more preferably 25～90 mass %, more preferably 30 ～85 mass %, the most preferably 35～80 mass %.
As resin contained in compositions (y), the tree as the resin contained by above-mentioned composition (x) can be enumerated Fat, preferably comprises the resin identical with compositions (x).It should be noted that these resins can be used alone, it is also possible to combination Two or more uses.
It addition, as more specifically resin contained in compositions (y), preferably there is the resin of functional group, more preferably go up State the acrylic resin (A) with functional group, the most above-mentioned acrylic copolymer (A1).
Relative to the total amount (100 mass % (the most not including retarder thinner)) of compositions (y), the tree in compositions (y) Fat content is usually 1～85 mass %, preferably 5～80 mass %, more preferably 10～75 mass %, and more preferably 20 ～70 mass %, the most preferably 25～65 mass %.
It addition, as the cross-linking agent contained in compositions (y), the crosslinking contained in above-mentioned resin portion (X) can be enumerated Agent, preferably comprises more than a kind in metal-chelating species cross-linking agent and epoxies cross-linking agent, more preferably contains metal-chelating Species cross-linking agent.Additionally, it is preferred that contain metal-chelating species cross-linking agent and epoxies cross-linking agent simultaneously.
It should be noted that contain metal-chelating species cross-linking agent and the feelings of epoxies cross-linking agent in compositions (y) simultaneously Under condition, preferred content ratio (mass ratio) scope of metal-chelating species cross-linking agent and epoxies cross-linking agent and above-mentioned composition X () is identical.
Relative to resin 100 mass parts contained in compositions (y), the content of cross-linking agent is preferably 0.01～15 mass Part, more preferably 0.1～10 mass parts, more preferably 0.3～7 mass parts.
The forming method of (film (x '), (y '))
It should be noted that when forming film, for ease of forming film, preferably coordinate in compositions (x) and (y) Solvent and make the form of the solution of compositions.
As such solvent, water, organic solvent etc. can be enumerated.
As this organic solvent, can enumerate such as: toluene, ethyl acetate, butyl acetate, butanone, methyl-isobutyl Ketone, methanol, ethanol, isopropanol, the tert-butyl alcohol, sec-butyl alcohol, acetylacetone,2,4-pentanedione, Ketohexamethylene, normal hexane, hexamethylene etc..Need explanation It is that these solvents can be used alone, or is applied in combination two or more.
The laminated layer sequence of the film (x ') that formed in this operation and (y ') is not particularly limited, preferably with on film (y ') The mode of multi-layer coating film (x ') is formed.
As film (x ') and the forming method of (y '), can be after forming film (y ') on film (y ') successively The method forming film (x '), it addition, from the viewpoint of productivity, it is also possible to it is to be coated with film with multilayer coater simultaneously (y ') and film (x ') and the method that formed.
As the coating machine used when sequentially forming, can enumerate such as: spin coater, flush coater, bar coater, scraper for coating Machine, roll coater, roller cutter coating machine, scraper plate coating machine, gravure coating machine, curtain are coated with machine, die coating machine etc..
As the coating machine using multilayer coater to be used when being coated with simultaneously, can enumerate such as: curtain is coated with machine, mould Painting machine etc., wherein, from the viewpoint of operability, preferably die coating machine.
It should be noted that in this operation (1), can at least one in forming film (x ') and film (y ') it Rear and before being transferred to operation (2), do not make this film carry out the pre-dried of degree of curing reaction.
As baking temperature when carrying out this pre-dried in this operation (1), generally can not send out at the film formed Suitably set within the temperature range of the degree of raw solidification, the preferably shorter than baking temperature in operation (2).As " less than operation (2) In baking temperature " the concrete baking temperature represented by restriction, preferably 10～45 DEG C, more preferably 10～34 DEG C, enter one Step is preferably 15～30 DEG C.
＜ operation (2) ＞
Operation (2) is the operation that the film (x ') making to be formed in operation (1) and film (y ') are simultaneously dry.
In this operation, by making the film (x ') of formation and film (y ') be dried simultaneously, can be formed and comprise resin portion (X) and the resin bed of particle fraction (Y), simultaneously upper on the surface (α) of this resin bed multiple recesses are formed.
As the baking temperature in this operation, from easily forming the idiomorphism by resin bed on the surface (α) of resin bed From the viewpoint of the unbodied recess become and formed, preferably 35～200 DEG C, more preferably 60～180 DEG C, further preferably It is 70～160 DEG C, the most preferably 80～140 DEG C.
When this baking temperature is more than 35 DEG C, it is possible to obtain the bonding sheet that de-gas is good.On the other hand, it is dried at this When temperature is less than 200 DEG C, it is possible to base material, release liner that suppression bonding sheet is had shrink such unfavorable condition.
It should be noted that this baking temperature is the lowest, the difference of height of the recess of formation is the biggest, but the quantity of the recess formed The trend being reduced.
It should be noted that the periphery of the particle fraction (Y) at the resin bed formed by this operation, space can be formed Partly (Z).
By using more than a kind in silicon dioxide granule, metal oxide particle and smectite as above-mentioned group Microgranule contained in compound (y), can be readily formed gap (Z).
It addition, manufacturing the bonding as bonding sheet 1a～2b of Fig. 1 with the resin bed being formed with multiple structure In the case of sheet, the manufacture method of the 1st and the 2nd mode the most shown below, described multiple structure is that lamination mainly contains successively There are the layer (X β) of resin portion (X), the layer (Y1) containing particle fraction (Y) more than 15 mass % and mainly contain resin The partly layer (X α) of (X).
It should be noted that in the record of the manufacture method of the 1st and the 2nd following mode, " containing resin as main one-tenth Point compositions (x β) or (x α) " identical with above-mentioned composition (x), each composition of containing in compositions (x β) or (x α) detailed Situation (composition kind, preferred component, component content etc.) is the most identical.And, " comprise the compositions of the microgranule of more than 15 mass % (y) " also as described above.
(manufacture method of the 1st mode)
As the manufacture method of the 1st mode, at least there is following operation (1A) and (2A).
Operation (1A): on base material or release liner successively lamination and form film (x β '), film (y ') and film (x α ') operation, described film (x β ') is formed as the compositions (x β) of main constituent by containing resin, and described film (y ') is by institute The compositions (y) stating microgranule more than containing 15 mass % is formed, described film (x α ') by containing resin as the group of main constituent Compound (x α) is formed
Operation (2A): make the work that the film (x β ') formed in operation (1A), film (y ') and film (x α ') are dried simultaneously Sequence
In operation (1A), in compositions (x β), compositions (y) and compositions (x α), preferably coordinate above-mentioned solvent, It is coated after the form of the solution forming compositions.
As film (x β '), film (y ') and the forming method of film (x α '), can be use above-mentioned coating machine with After forming film (x β ') on base material or release liner, film (x β ') forms film (y '), and then on film (y ') Form the method that the mode of film (x α ') carries out sequentially forming, it is also possible to be to use above-mentioned multilayer coater to be coated with film simultaneously (x β '), film (y ') and film (x α ') and the method that formed.
It should be noted that in this operation (1A), 1 in forming film (x β '), film (y ') and film (x α ') After the above film of layer and before being transferred to operation (2A), it is possible to implement do not make this film carry out the predry of degree of curing reaction Dry process.
For example, it is possible on carrying out respectively after each film of film (x β '), film (y ') and film (x α ') is formed State pre-dried, it is also possible to together with after film (x β ') and film (y ') are formed, carry out above-mentioned pre-dried, the most again Form film (x α ').
As baking temperature when carrying out this pre-dried in this operation (1A), generally can not send out at the film formed Suitably set within the temperature range of the degree of raw solidification, the preferably shorter than baking temperature in operation (2A).As " less than operation (2A) baking temperature in " the concrete baking temperature represented by restriction, preferably 10～45 DEG C, more preferably 10～34 DEG C, More preferably 15～30 DEG C.
Operation (2A) is the work that film (x β '), film (y ') and the film (x α ') making to be formed in operation (1A) is simultaneously dry Sequence, the preferred scope of the baking temperature in this operation is identical with above-mentioned operation (2).By this operation, can be formed and comprise resin Partly (X) and the resin bed of particle fraction (Y).
(manufacture method of the 2nd mode)
As the manufacture method of the 2nd mode, at least there is following operation (1B) and (2B).
Operation (1B): on the layer (X β) mainly containing resin portion (X) being arranged on base material or release liner successively Lamination and form film (y ') and the operation of film (x α '), described film (y ') is by the described microgranule containing more than 15 mass % Compositions (y) formed, described film (x α ') is formed as the compositions (x α) of main constituent by containing resin
Operation (2B): the operation that the film that makes to be formed in operation (1B) (y ') and film (x α ') are dried simultaneously
In operation (1B), " mainly containing the layer (X β) of resin portion (X) " can to above-mentioned by containing resin as master The film (x β ') that the compositions (x β) of composition is formed is dried and is formed.
Layer (X β) is formed by compositions (x β), therefore, in addition to the resins, can also contain cross-linking agent, leads in layer (X β) With additive etc..As the content of the resin portion (X) in layer (X β), as mentioned above.
As the forming method of layer (X β), can be formed on base material or release liner by containing hydrocarbon resins as main one-tenth The film (x β ') that the compositions (x β) divided is formed, and make this film (x β ') be dried and be formed.
As baking temperature now, it is not particularly limited, preferably 35～200 DEG C, more preferably 60～180 DEG C, enters One step is preferably 70～160 DEG C, the most preferably 80～140 DEG C.
It should be noted that in the manner, be not on film (x β '), but layer (X β) obtained after the drying On sequentially form film (y ') and film (x α '), different from above-mentioned 1st mode in this.
In operation (1B), in compositions (y) and compositions (x α), preferably coordinate above-mentioned solvent, making compositions It is coated after the form of solution.
As film (y ') and the forming method of film (x α '), can be to use above-mentioned coating machine with in the upper shape of layer (X β) Form, on film (y '), the method that the mode of film (x α ') sequentially forms the most again, it is also possible to be on using after becoming film (y ') State multilayer coater and be coated with film (y ') and film (x α ') and the method that formed simultaneously.
It should be noted that in this operation (1B), can be after forming film (y ') or form film (y ') and painting After film (x α ') and be transferred to before operation (2B) to implement not make the pre-dried of degree that this film carries out curing reaction.
As baking temperature when carrying out this pre-dried in this operation (1B), generally can not send out at the film formed Suitably set within the temperature range of the degree of raw solidification, the preferably shorter than baking temperature in operation (2B).As " less than operation (2B) baking temperature in " the concrete baking temperature represented by restriction, preferably 10～45 DEG C, more preferably 10～34 DEG C, More preferably 15～30 DEG C.
Operation (2B) is the film (y ') making to be formed in operation (1B) and the simultaneously dry operation of film (x α '), this operation In the preferred scope of baking temperature identical with above-mentioned operation (2).By this operation, can be formed containing resin portion (X) and The resin bed of particle fraction (Y).
(viscoelastic layer)
The present invention also provides for a kind of viscoelastic layer, and it comprises the multilayer structure making of more than 3 layers, the multilamellar of described more than 3 layers Structure comprises containing fine-grained containing particulate layer, and wherein, this contains particulate layer and is formed at beyond the outermost layer of this viscoelastic layer, and this glues There is recess at least one surface of elastic layer, and this recess be shaped as amorphous.
The viscoelastic layer of one mode of the present invention preferably comprises resin portion (X) and particle fraction (Y), described resin portion Dividing (X) containing resin as main constituent, described particle fraction (Y) is made up of microgranule.
Constitute the kind of resin of viscoelastic layer and content, the kind of microgranule and content, the kind of other composition and content, And constitutive requirements relevant with viscoelastic layer (Rotating fields of the multilayer structure making important document relevant with recess, thickness, formation material Material, manufacture method etc.) identical with the constitutive requirements described in the project of above-mentioned resin bed.
Wherein, the surface of viscoelastic layer can also have cohesive.Accordingly, as the resin of composition viscoelastic layer, Can also only use non-adhesive resin.
Embodiment
By below example, the present invention is specifically described, but the present invention is not limited to below example.Need The physics value being noted that in following manufacture example and embodiment is the value recorded by the following method.
Weight average molecular weight (Mw) ＞ of ＜ resin
Use gel permeation chromatography device (TOSOH Co., Ltd manufacture, ProductName " HLC-8020 "), under the following conditions Measure the value going forward side by side column criterion polystyrene conversion and record.
(condition determination)
Chromatographic column: by " TSK guard column HXL-L " " TSK gel G2500HXL " " TSK gel G2000HXL " " TSK gel G1000HXL " (be TOSOH Co., Ltd manufacture) chromatographic column of being connected in sequence
Column temperature: 40 DEG C
Eluting solvent: oxolane
Flow velocity: 1.0mL/min
Mensuration ＞ of the volume average secondary particle diameter of ＜ silicon dioxide granule
The volume average secondary particle diameter of silicon dioxide granule is to use Multisizer 3 (Beckman Coulter company Manufacture) utilize the mensuration of the particle size distribution of coulter counter method to obtain by carrying out.
Mensuration ＞ of the thickness of ＜ resin bed
The thickness of resin bed uses scanning electron microscope, and (Hitachi Co., Ltd manufactures, ProductName " S- 4700 "), observe the resin bed cross section as the bonding sheet of object to be measured.
Manufacture example x-1～6
(solution (x-1) of resin combination～the preparation of (x-6))
In the kind recorded to table 1 and solution 100 mass parts of the acrylic resin of solid constituent amount, interpolation table 1 is remembered The kind carried and the cross-linking agent of use level and retarder thinner, be prepared for the resin group of solid component concentration described in table 1 respectively The solution (x-1) of compound～(x-6).
It should be noted that each one-tenth that the table 1 that the preparation of the solution of resin combination (x-1)～(x-6) is used is recorded The details divided is as described below.
The solution ＞ of ＜ acrylic resin
Solution (i): (have containing acrylic resin (x-i) and be derived from butyl acrylate (BA) and acrylic acid (AA) The acrylic copolymer of construction unit, BA/AA=90/10 (quality %), Mw:47 ten thousand) and solid component concentration be 33.6 matter The toluene of amount % and the mixed solution of ethyl acetate.
Solution (ii): (have containing acrylic resin (x-ii) and be derived from butyl acrylate (BA), acrylic acid 2-ethyl The acrylic copolymer of the construction unit of own ester (2EHA), vinyl acetate (VAc) and acrylic acid (AA), BA/2EHA/VAc/ AA=46/37/10/7 (quality %), Mw:37 ten thousand) and toluene that solid component concentration is 43.0 mass % and ethyl acetate is mixed Close solution.
＜ cross-linking agent ＞
Aluminium chelate compound class cross-linking agent: ProductName " M-5A ", Zong Yan KCC manufactures, solid component concentration= 4.95 quality %.
Epoxies cross-linking agent: by dilute with toluene to " TETRAD-C " (ProductName, Mitsubishi Gas Chemical Co., Ltd manufactures) Release, make the epoxies cross-linking agent solution that solid component concentration is 5 mass %.
Isocyanates cross-linking agent: ProductName " Coronate L ", TOSOH Co., Ltd manufactures, solid component concentration= 75 mass %.
Aziridines cross-linking agent: ProductName " BXX5134 ", TOYOCHEM company manufactures, solid component concentration=5 matter Amount %.
＜ retarder thinner ＞
IPA: isopropanol (IPA).
AcOEt: ethyl acetate.
Manufacture example y-0
(preparation of particle dispersion liquid (y-0))
(it is derived from butyl acrylate (BA) and acrylic acid containing having to the solution (i) containing acrylic resin (x-i) (AA) acrylic copolymer (BA/AA=90/10 (quality %), Mw:47 ten thousand) of construction unit and solid component concentration are The toluene of 33.6 mass % and the mixed solution of ethyl acetate) 100 mass parts (solid constituent: 33.6 mass parts) middle interpolation conduct (ProductName " Nipsil E-200A ", TOSOH SILICA company manufactures, volume average secondary grain for the silicon dioxide granule of microgranule Footpath: 3 μm) 50.4 mass parts (solid constituent: 50.4 mass parts), and add toluene, make microgranule disperse, be prepared for containing propylene Acid resin and silicon dioxide granule and the particle dispersion liquid (y-0) that solid component concentration is 30 mass %.
Manufacture example y-1～8
(film (y ') formed with coating fluid (y-1)～the preparation of (y-8))
Add described in table 2 in particle dispersion liquid (y-0) prepared by manufacture example y-0 of the use level described in table 2 The solution of the acrylic resin of kind and use level, cross-linking agent and retarder thinner, be prepared for the solid constituent that table 2 is recorded respectively The film of concentration (y ') formed with coating fluid (y-1)～(y-8).
Described in the table 2 that the preparation of (y ') formation coating fluid (y-1)～(y-8) is used it should be noted that film The details of each composition as described below.
The solution ＞ of ＜ acrylic resin
Solution (i): acrylic resin (x-i) (details is described above).
＜ cross-linking agent ＞
Aluminium chelate compound system cross-linking agent: ProductName " M-5A ", Zong Yan KCC manufactures, solid component concentration= 4.95 quality %.
Epoxies cross-linking agent: by dilute with toluene to " TETRAD-C " (ProductName, Mitsubishi Gas Chemical Co., Ltd manufactures) Release, make the epoxies cross-linking agent solution that solid component concentration is 5 mass %.
＜ retarder thinner ＞
IPA: isopropanol (IPA).
IPA/CHN: the mixed solvent (IPA/CHN=60/40 (matter being made up of isopropanol (IPA) and Ketohexamethylene (CHN) Amount ratio)).
Embodiment 1～8
(1) formation of film
Use one side be provided with aluminium-vapour deposition layer polyethylene terephthalate (PET) film (Lindeke Co., Ltd manufacture, ProductName " FNS MATT N50 ", thickness 50 μm) as base material.
Spreader is used to be coated with the solution (x-manufacturing resin combination prepared by example x-1 on the aluminium-vapour deposition layer of this PET film 1) so that the coating thickness (coating thickness of non-dry state) after coating reaches the thickness shown in table 3, defines film (x β’)。
Then, spreader is used to be coated with in film (y ') is formationed of kind shown in the film (x β ') formed upper coating table 3 Any one in liquid (y-1)～(y-4) so that 2 layers of gross thickness (non-dry of film (x β ') and film after coating (y ') again 2 layers of gross thickness of state) reach the thickness shown in table 3, define film (y ').
Then, spreader is used to manufacture the solution of resin combination prepared by example x-1 in the upper coating of the film (y ') formed (x-1) so that film (x β '), film (y ') and 3 layers of gross thickness (3 layers of non-dry state of film (x α ') after coating again Gross thickness) reach the thickness shown in table 3, define film (x α ').
(2) dried
Then, the film (x β '), film (y ') and the film (x α ') that make 3 layers are dried 2 points at baking temperature 100 DEG C simultaneously Clock, has made the bonding sheet with following resin bed, and described resin bed comprises resin portion (X) and particle fraction (Y), and has Thickness shown in table 3.
Embodiment 9
Use one side be provided with aluminium-vapour deposition layer PET film (Lindeke Co., Ltd manufacture, ProductName " FNS MATT N50 ", Thickness 50 μm) as base material.
Knife type coater is used be coated with the molten of the manufacture resin combination prepared of example x-2 on the aluminium-vapour deposition layer of this PET film Liquid (x-2) so that the thickness (thickness of the film of non-dry state) of the film after coating reaches 25 μm, defines film (x β’).Then, it is dried 2 minutes at baking temperature 100 DEG C, defines the layer (X β) containing resin portion (X).And then, with by shape (Lindeke Co., Ltd's manufacture, ProductName " SP-PET381031 ", one side is provided with poly-silicon for the surface of the layer (X β) become and stripping film The PET film of oxygen alkanes peeling agent layer, thickness 38 μm) the mode of peeling agent layer surface laminating be laminated, made and there is layer The laminated body of (X β).
Then, use multilayer coater (width: 500mm) having peeled off stripping film of above-mentioned laminated body exposing surface The coating simultaneously on the surface of layer (X β) manufactures film (y ') is formationed coating fluid (y-1) and manufacture example x-1 prepared by example y-1 The solution (x-1) of resin combination of preparation, has concurrently formed film (y ') and film (x α ') on layer (X β) successively.Need Illustrate, in the setting of multilayer coater, the thickness of film (y ') is set to 55 μm, the thickness of film (x α ') is set to 65 μm, thus define each film.
Then, the films of 2 layers (y ') and film (x α ') are dried 2 minutes at baking temperature 100 DEG C simultaneously, make Having the bonding sheet of following resin bed, described resin bed comprises resin portion (X) and particle fraction (Y), and has shown in table 3 Thickness.
Comparative example 1
In embodiment 1, do not form film (y ') and film (x α '), use knife type coater at the PET film as base material Aluminium-vapour deposition layer on coating manufacture the solution (x-1) of resin combination prepared by example x-1 so that dried thickness is 25 μm, Form film (x β '), in addition, made similarly to Example 1 and there is thickness 25 μm only formed by resin portion (X) The bonding sheet of resin bed.
Comparative example 2
Use one side be provided with aluminium-vapour deposition layer PET film (Lindeke Co., Ltd manufacture, ProductName " FNS MATT N50 ", Thickness 50 μm) as base material.
Spreader is used to be coated with the solution (x-manufacturing resin combination prepared by example x-1 on the aluminium-vapour deposition layer of this PET film 1), define film (x β '), be then dried 2 minutes at 100 DEG C, define the layer of thickness 5 μm comprising resin portion (X) (Xβ)。
Different from above-mentioned, (Lindeke Co., Ltd manufactures, ProductName " SP-at stripping film to use spreader PET381031 ", one side is provided with the PET film of polysiloxane-based peeling agent layer, thickness 38 μm) peeling agent layer on coating manufacture example Film prepared by y-1 (y ') formation coating fluid (y-1), defines film (y '), is then dried 2 minutes at 100 DEG C, is formed The layer (Y1) of thickness 15 μm containing resin portion (X) and particle fraction (Y).
It addition, different from above-mentioned, use spreader to be coated with fabric on the peeling agent layer of the stripping film of kind same as described above Make the solution (x-1) of resin combination prepared by example x-1, define film (x α '), be then dried 2 minutes at 100 DEG C, shape Become the layer (X α) of thickness 5 μm containing resin portion (X).
Then, using by the surface of the layer (X β) formed on the PET film of base material and layer (Y1) formed as discussed above The surface exposed laminating mode be laminated.Further with the layer (Y1) that the stripping film eliminated on layer (Y1) is exposed The mode fitted of the surface exposed of surface and layer (X α) formed as discussed above be laminated.
Thus, having made on base material lamination successively has layer (X β), layer (Y1) and a layer (X α), and has and comprise resin portion And the bonding sheet of resin bed of thickness 25 μm of particle fraction (Y) (X).
Embodiment 10～16
Use one side be provided with aluminium-vapour deposition layer PET film (Lindeke Co., Ltd manufacture, ProductName " FNS MATT N50 ", Thickness 50 μm) as base material.
By multilayer coater (width: 250mm), with the flow shown in table 4 and coating speed at the aluminium-vapour deposition of this PET film On layer, use any one manufactured in example x-1～the solution (x-1) of 6 resin combinations prepared～(x-6) and manufacture example y-1 ～8 preparation film (y ') formation coating fluid (y-1)～(y-8) in any one be coated simultaneously, from substrate side by Concurrently form according to film (x β '), film (y ') and the order of film (x α ').
It should be noted that the solution of resin combination used as the forming material of each film and film (y ') shape The kind of one-tenth coating fluid is as described in table 4.
Then, the films of 3 layers (x β '), film (y ') and film (x α ') are dried 2 minutes at baking temperature 100 DEG C, And make it be dried simultaneously, make to have and comprise resin portion (X) and particle fraction (Y) and there is the resin of thickness shown in table 4 The bonding sheet of layer.
Embodiment 17
Use multilayer coater (width: 250mm), using the flow shown in table 4 and coating speed as the 1st release liner Stripping film (Lindeke Co., Ltd manufacture, ProductName " SP-PET381031 ", thickness 38 μm, the one side at PET film is provided with poly- Type siloxane peeling agent layer) peeling agent layer on the most simultaneously coating manufacture example 3 preparation resin combination solution (x-3), Manufacture film (y ') is formationed coating fluid (y-5) prepared by example y-5 and the solution (x-of resin combination prepared by manufacture example x-3 3), concurrently form according to film (x β '), film (y ') and the order of film (x α ') from stripping film side.
Then, the film (x β ') of 3 layers, film (y '), film (x α ') are dried 2 points at baking temperature 100 DEG C simultaneously Clock, defines the resin bed of the thickness shown in table 4 comprising resin portion (X) and particle fraction (Y).Then, with in formation The surface (α) of resin bed is upper, and (Lindeke Co., Ltd manufactures, ProductName " SP-with the stripping film as the 2nd release liner PET386040 ") release liner layer surface laminating mode be laminated, made without base material bonding sheet.
Then, this is stood 1 week without base material bonding sheet under 23 DEG C of environment, then remove the 1st release liner, with expose (Lindeke Co., Ltd manufactures, ProductName " FNS for the surface (β) of resin bed and the PET film being provided with aluminium-vapour deposition layer as base material MATT N50 ", thickness 50 μm) aluminium-vapour deposition layer surface laminating mode be laminated, made the bonding sheet with base material.
Embodiment 18
Use one side be provided with aluminium-vapour deposition layer PET film (Lindeke Co., Ltd manufacture, ProductName " FNS MATT N50 ", Thickness 50 μm) as base material.
Knife type coater is used be coated with the molten of the manufacture resin combination prepared of example x-1 on the aluminium-vapour deposition layer of this PET film Liquid (x-1), defines film (x β ').Then, it is dried 2 minutes at baking temperature 100 DEG C, defines containing resin portion (X) The layer (X β) of thickness 8 μm.And then, with surface and the stripping film of layer (X β) that will be formed, (Lindeke Co., Ltd manufactures, product Name " SP-PET381031 ", one side is provided with the PET film of polysiloxane-based peeling agent layer, thickness 38 μm) the surface of peeling agent layer The mode of laminating is laminated, and has made the laminated body with layer (X β).
Then, use multilayer coater (width: 500mm), fold above-mentioned stripping with the flow shown in table 4 and coating speed The layer stripping film of body and on the surface of layer (X β) exposed coating the most simultaneously manufacture film prepared by example y-1 (y ') is formationed painting Cloth liquid (y-1) and manufacture the solution (x-1) of resin combination prepared by example x-1, according to film (y ') and be coated with from layer (X β) side The order of film (x α ') has carried out lamination simultaneously.
Then, the films of 2 layers (y ') and (x α ') are dried 2 minutes at baking temperature 100 DEG C simultaneously, have made and had Comprise the bonding sheet with base material of the resin bed of thickness shown in the table 4 of resin portion (X) and particle fraction (Y).
For the resin bed of each bonding sheet that embodiment and comparative example make, observe as follows or determine table Whether exist on face (α) recess, whether be the shape of recess on unbodied judgement, surface (α), there is position, sticking veneer Shape and the quality retention of resin bed.These results are shown in table 3 and table 4.
Unbodied recess ＞ whether is there is on ＜ surface (α)
On the resin layer surface (α) of the bonding sheet made in embodiment and comparative example, arbitrarily selecting 10 length of sides is 4mm Square area defined (R), observe by the naked eye with digit microscope (Keyence company manufacture, product is entitled " Digital Microscope VHX-5000 ", multiplying power: 50 times) overlook (carrying out stereovision as required) from surface (α) side The shape of the recess existed in observing each region (R), is confirmed whether to there is unbodied recess.
It should be noted that in the case of confirming multiple recess by above-mentioned observation in 10 selected regions, Aperiodicity (important document (IV)) and sticking veneer are equipped with for the quantity of recess in 10 selected regions, the presence bit of recess Shape confirmed the most together.
Shape ＞ of the recess on ＜ surface (α)
It addition, in the specific region limited by each important document on the resin layer surface (α) of this bonding sheet, use scanning electricity (Hitachi Co., Ltd manufactures sub-microscope, and ProductName " S-4700 " is seen by multiplying power 30 again for important document (II) Examine) observed whether defining the recess meeting following important document (I)～(III).
In table 3 and table 4, it is judged that be recited as " A " for defining the situation of the recess meeting each important document, it is judged that for unconfirmed It is recited as " F " to the situation that there is the recess meeting each important document.
Important document (I): in the square area defined (P) that surface (α) upper optional length of side is 5mm, exist The recess of multiple differences of height with more than maximum 0.5 μm.
Important document (II): exist in the square area defined (P) that surface (α) upper optional length of side is 5mm The recess of multiple differences of height with more than maximum 0.5 μm, and relative to the sum (100%) of the plurality of recess, have the most not The number of the recess of identical shape is more than 95%, and (in the situation of 100%, i.e. region (P), all of recess has the most not phase The situation of similar shape is being " A+ " described in table).
Important document (III): in the square area defined (Q) that surface (α) upper optional length of side is 1mm, deposit There is more than 1 the recess of the difference of height of more than maximum 0.5 μm.
It should be noted that the maximum in the value of the difference of height of the multiple recesses measured when will evaluate important document (I) is made It is recorded in table 3 and table 4 for " maximum of difference of height ".
Quality retention ＞ of the resin bed of ＜ bonding sheet
For the embodiment beyond embodiment 17 and comparative example, with stripping film, (Lindeke Co., Ltd manufactures, product Name " SP-PET381031 ", one side is provided with the PET film of polysiloxane-based peeling agent layer, thickness 38 μm) replace above-mentioned base material, and Defining resin bed according to the method for each embodiment and comparative example on the surface of the peeling agent layer of this stripping film, then removing should Stripping film, has obtained single resin bed.
It addition, for embodiment 17, by during 2 stripping films removings of bonding sheet without base material of making, obtain Single resin bed.
Then, the quality of the resin bed before heating is determined, then this resin bed is put into Muffle furnace (DENKEN Company manufactures, ProductName " KDF-P90 ") in, at 800 DEG C, heated 30 minutes.Then, the quality to the resin bed after heating It is measured, is calculated the quality retention of resin bed by following formula.
The quality retention (%) of resin bed=[quality of the resin bed after heating]/[quality of the resin bed before heating] ×100
Each bonding sheet that embodiment and comparative example are made, based on following methods to " de-gas ", " resistant blister " and " bonding force " is determined or evaluates.These results are shown in table 3 and table 4.
＜ de-gas ＞
The bonding sheet of vertical 50mm × horizontal 50mm size is pasted on the tripolycyanamide coated plate as adherend, and makes Produce residual air.Then, remain with or without air using to observe after squeegee pressure viscosity, each bonding according to following benchmark evaluation The de-gas of sheet.
A: residual air disappears, and de-gas is excellent.
F: residual air still remains, de-gas is poor.
＜ resistant blister ＞
The bonding sheet of vertical 50mm × horizontal 50mm size is pasted on the polymethyl of vertical 70mm × horizontal 150mm × thickness 2mm Acid methyl ester plate (Mitsubishi Rayon Co., Ltd manufactures, ProductName " ACRYLITE L001 "), uses squeegee to carry out pressure viscosity, makes Test specimen.
This test specimen is stood 12 hours at 23 DEG C, then in the air drier of 80 DEG C, stands 1.5 hours, enter One step stands 1.5 hours in the air drier of 90 DEG C, observes by the naked eye the foaming generation state after heating promotes, according to The following benchmark evaluation resistant blister of each bonding sheet.
A: entirely without confirming foaming.
B: local confirms foaming.
C: confirm foaming on whole.
＜ bonding force ＞
The bonding sheet that embodiment and comparative example make is cut into the size of vertical 25mm × horizontal 300mm, then by this bonding The surface (α) of the resin bed of sheet 23 DEG C, be pasted in the environment of 50%RH (relative humidity) corrosion resistant plate (SUS304, No. 360 Grind), under equivalent environment, stand 24 hours.After standing, based on JIS Z0237:2000, by 180 ° of stripping methods to stretch speed Degree 300mm/ divides the bonding force to each bonding sheet to be determined.
According to table 3 and table 4, can confirm that the bonding sheet that embodiment 1～18 makes meets above-mentioned wanting in surface (α) upper existence Part (I)～(III) and the recess formed by the self-forming of resin bed, its de-gas, resistant blister and bonding force are the best Good.
It should be noted that for any one in the bonding sheet that embodiment 1～18 makes, use above-mentioned scanning Ultramicroscope (multiplying power: 30 times) is to when observing in the region (P) on surface (α), it is thus identified that being shaped as of multiple recesses Amorphous, and the plurality of recess do not has given pattern, is formed not by the transfer of embossed pattern.Additionally confirm Arrive, in the cross section of the thickness direction of resin bed, containing the border between particulate layer and other layer not with base material or release liner , there is the intensive part of microgranule containing particulate layer intermittently in the horizontal plane direction of base material or release liner and do not deposit in plane-parallel Part at microgranule.Additionally, observe by the naked eye, from surface (α) side exposed, the recess confirming to be present in surface (α) Unbodied shape.
It addition, by above-mentioned observation, the shape being present in the sticking veneer in the region (P) on surface (α) is also nothing Setting.
Additionally, for any one in the bonding sheet that embodiment 1～18 makes, all confirm and there is following shape Shape: be present in 1 in the region (Q) on resin layer surface (α) limit extended to as this region (Q) boundary line using upper recess Foursquare any one side of a length of 1mm, and extend to continuously by the pros that the length of side be 1mm adjacent with this region (Q) Other region that shape is surrounded (Q ') in.This can also be by the solid of the resin layer surface (α) of such as Fig. 4 (b) and Fig. 5 (b) Image confirms.
Fig. 4 and Fig. 5 is the figure during bonding sheet observing embodiment 1 and embodiment 10 making by scanning electron microscope respectively Picture, (a) is the cross-sectional image of this bonding sheet, and (b) is the stereo-picture of the resin layer surface (α) of this bonding sheet.Need explanation It is that, in the image of Fig. 4 (a), in this image, 10 scales described in bottom right represent the length of 20.0 μm, at the figure of Fig. 4 (b) In Xiang, in this image, 10 scales described in bottom right represent the length of 1.00mm.It addition, in the image of Fig. 5 (a), this figure In Xiang, 10 scales described in bottom right represent the length of 200 μm, in the image of Fig. 5 (b), in this image described in bottom right 10 scales represent the length of 1.00mm.
The image of Fig. 4 and Fig. 5 shows present on the resin layer surface (α) of the bonding sheet that embodiment 1 and 10 makes recessed The shape in portion, the recess cross sectional shape of the bonding sheet of other embodiments, recess shape when observing from surface (α) side of resin bed Shape, sticking veneer shape also identical with Fig. 4 and image illustrated in fig. 5.
On the other hand, the surface of resin bed that the bonding sheet that comparative example 1 and 2 makes is had is unconfirmed to specific recess Formed, result in the result of de-gas difference.It addition, the bonding sheet of comparative example 1 also results in the result of resistant blister difference.
Fig. 6 is the image during bonding sheet with sem observation comparative example 1 making, and (a) is this bonding sheet Cross-sectional image, (b) is the stereo-picture of the resin layer surface (α) of this bonding sheet.It should be noted that institute in the image of Fig. 6 (a) 10 scales recorded represent the length of 20.0 μm, and 10 scales described in the image of Fig. 6 (b) represent the length of 1.00mm Degree.
Image as shown in Figure 6, the resin layer surface (α) of the bonding sheet that comparative example 1 makes does not finds the formation of recess.
Industrial applicibility
The bonding sheet of one mode of the present invention is as identifying or purposes, metallic plate etc. are blocked in decorative use, application The big bonding sheet of the bonding area of surface protection purposes etc. be useful.

Claims (18)

1. a bonding sheet, it has resin bed on base material or release liner, and the most described resin bed be provided with described The surface (α) of the opposition side, side of base material or release liner has cohesive, and described resin bed comprises the multiple structure of more than 3 layers Body, the multilayer structure making of described more than 3 layers comprise the microgranule more than containing 15 mass % containing particulate layer, wherein,
Described it is formed at beyond the outermost layer of described resin bed containing particulate layer,
There is recess on surface (α), and described recess be shaped as amorphous.
Bonding sheet the most according to claim 1, wherein, described recess is the self-forming by described resin bed and is formed 's.
Bonding sheet the most according to claim 1 and 2, wherein, in the cross section of the thickness direction of described resin bed, described contains The border of particulate layer and other layer not with described base material or the plane-parallel of release liner.
4. according to the bonding sheet according to any one of claims 1 to 3, wherein, described recess does not have given pattern.
5. according to the bonding sheet according to any one of Claims 1 to 4, wherein, surface (α) exists multiple described recess.
Bonding sheet the most according to claim 5, wherein, the existence position of the plurality of recess does not have periodically.
7. according to the bonding sheet according to any one of claim 1～6, wherein, described containing particulate layer in described base material or stripping There is the intensive part of described microgranule on the horizontal plane direction of material intermittently and there is not the part of microgranule.
8. according to the bonding sheet according to any one of claim 1～7, wherein, described microgranule is selected from silicon dioxide granule, gold Belong to more than a kind in oxide particle and smectite.
9. according to the bonding sheet according to any one of claim 1～8, wherein, the average aggregate particle size of volume of described microgranule is Below 50 μm.
10. according to the bonding sheet according to any one of claim 1～9, wherein, it is possible to from exposing surface (α) side on surface Observe by the naked eye the amorphous shape confirming to be present in the described recess on surface (α).
11. according to the bonding sheet according to any one of claim 1～10, wherein, described containing other layer beyond particulate layer is By comprising the layer that the resin content as main constituent and microgranule is formed less than the compositions of 15 mass %.
12. according to the bonding sheet according to any one of claim 1～11, and wherein, described resin bed is formed with multiple structure, institute State multiple structure be from the side being provided with base material or release liner successively lamination mainly contain resin portion (X) layer (X β), Containing particle fraction (Y) more than 15 mass % containing particulate layer (Y1) and the layer (X α) that mainly contains resin portion (X) and Become.
13. bonding sheets according to claim 12, wherein, described resin portion (X) is handed over containing selected from metal-chelating species In connection agent, epoxies cross-linking agent and aziridines cross-linking agent more than a kind.
14. according to the bonding sheet described in claim 12 or 13, wherein,
Layer (X β) is by the layer formed as the compositions (x β) of main constituent containing resin,
Layer (Y1) is the layer formed by the compositions (y) containing microgranules more than 15 mass %,
Layer (X α) is by the layer formed as the compositions (x α) of main constituent containing resin.
The manufacture method of 15. 1 kinds of bonding sheets, it is the method for the bonding sheet according to any one of manufacturing claims 1～13, The method at least has following operation (1) and (2),
Operation (1): form the operation of film (x ') and film (y '), described film (x ') by containing resin as the group of main constituent Compound (x) is formed, described film (y ') formed by the compositions (y) containing microgranules more than 15 mass %,
Operation (2): the operation that the film that makes to be formed in operation (1) (x ') and film (y ') are dried simultaneously.
The manufacture method of 16. 1 kinds of bonding sheets, it is the method for the bonding sheet described in manufacturing claims 14, and the method at least has There are following operation (1A) and (2A),
Operation (1A): on base material or release liner successively lamination and form film (x β '), film (y ') and film (x α ') Operation, described film (x β ') is formed as the compositions (x β) of main constituent by containing resin, described film (y ') contained by described The compositions (y) of microgranules more than 15 mass % is formed, described film (x α ') by containing resin as the compositions (x of main constituent α) formed,
Operation (2A): make the operation that the film (x β ') formed in operation (1A), film (y ') and film (x α ') are dried simultaneously.
The manufacture method of 17. 1 kinds of bonding sheets, it is the method for the bonding sheet described in manufacturing claims 14, and the method at least has There are following operation (1B) and (2B),
Operation (1B): lamination successively on the layer (X β) mainly containing resin portion (X) being arranged on base material or release liner And form film (y ') and the operation of film (x α '), and described film (y ') by the group of the described microgranule containing more than 15 mass % Compound (y) is formed, and described film (x α ') is formed as the compositions (x α) of main constituent by containing resin,
Operation (2B): the operation that the film that makes to be formed in operation (1B) (y ') and film (x α ') are dried simultaneously.
18. 1 kinds of viscoelastic layers, it comprises the multilayer structure making of more than 3 layers, the multilayer structure making of described more than 3 layers comprise containing Microgranule containing particulate layer, wherein,
Described it is formed at beyond the outermost layer of described viscoelastic layer containing particulate layer,
There is recess at least one surface of described viscoelastic layer, and this recess be shaped as amorphous.
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